Inner parting agents for producing self-parting moldings made of polyisocyanate polyaddition products

ABSTRACT

In a process for producing self-releasing, compact or cellular moldings which comprise polyisocyanate polyaddition products and may contain reinforcing material by reacting 
     a) organic and/or modified organic polyisocyanates with 
     b) at least one compound containing at least two reactive hydrogen atoms and having a molecular weight of from 62 to 10,000 and, if desired, 
     c) chain extenders and/or crosslinkers in the presence of 
     d) internal mold release agents and in the presence of or absence of 
     e) catalysts, 
     f) blowing agents, 
     g) reinforcing materials and 
     h) auxiliaries 
     in an open or closed mold, the internal mold release agents (d) used are diesters and/or monoesters of alkylsuccinic acids and/or diesters and/or monoesters of alkenylsuccinic acids.

Production of self-releasing, compact or cellular moldings whichcomprise polyisocyanate polyaddition products and may containreinforcing material, and internal mold release agents for this purpose.

The present invention relates to a process for producing self-releasing,compact or cellular moldings which comprise polyisocyanate polyadditionproducts and may contain reinforcing material by reacting

a) organic or modified organic polyisocyanates with

b) compounds containing at least two reactive hydrogen atoms and havinga molecular weight of from 62 to 10,000 and, if desired,

c) chain extenders and/or crosslinkers in the presence of

d) internal mold release agents and in the presence or absence of

e) catalysts,

f) blowing agents,

g) reinforcing materials and

h) auxiliaries

in an open or closed mold, wherein the internal mold release agents (d)used are diesters and/or monoesters of alkylsuccinic acids and/ordiesters and/or monoesters of alkenylsuccinic acids, and the use of thealkylsuccinic and/or alkenylsuccinic diesters or monoesters as internalmold release agents for moldings comprising polyisocyanate polyadditionproducts.

The production of moldings comprising compact or cellular polyisocyanatepolyaddition products which may contain reinforcing material, forexample compact or cellular elastomers containing urethane and/or ureagroups, known as polyurethane (PU) elastomers, and flexible, semirigidor rigid foams containing urethane and urea groups and possiblyisocyanurate groups, known as PU or polyisocyanurate (PIR) foams, byreacting organic and/or modified organic polyisocyanates with relativelyhigh molecular weight compounds containing at least two reactivehydrogen atoms, eg. polyoxyalkylenepolyamines and/or preferably organicpolyhydroxyl compounds having molecular weights of, for example, from500 to 12,000, and, if desired, low molecular weight chain extendersand/or crosslinkers in the presence or absence of catalysts, blowingagents, auxiliaries and/or additives in an open or closed mold is knownfrom numerous patent and literature publications. Appropriate selectionof the formative components, eg. the organic polyisocyanates, therelatively high molecular weight compounds containing hydrogen atomswhich react with NCO groups and possibly chain extenders and/orcrosslinkers enable elastic or rigid, compact or cellular moldingscomprising polyisocyanate polyaddition products and also allmodifications lying between these to be produced by this procedure.

An overview of the production of moldings comprising, for example,cellular or compact PU cast elastomers, PU elastomers, PU foams, PIRfoams, etc., their mechanical properties and their use is given, forexample, in the Kunststoff-Handbuch, Volume VII, “Polyurethane”, 1stedition, 1966, edited by Dr. R. Vieweg and Dr. A. Höchtlen, 2nd edition,1983, edited by Dr. G. Oertel and 3rd edition, 1993, edited by Dr. G. W.Becker and Dr. D. Braun (Carl-Hanser-Verlag, Munich, Vienna) and“Integralschaumstoffe”, edited by Dr. H. Piechota and Dr. H. Rohr(Carl-Hanser-Verlag, Munich, Vienna, 1975).

Although the production of compact or cellular, elastic or rigid PU orPIR moldings has achieved extraordinary industrial importance, theprocesses described also have technical deficiencies owing, for example,to the excellent adhesion of polyurethanes to other materials. Aparticular disadvantage is that the PU moldings adhere to the molds andare therefore difficult to remove therefrom, which frequently leads todamage to the molding, in particular to its surface. To avoid thisdisadvantage, use is generally made of polished metal molds, and/or theinternal surfaces of the molds are sprayed before production of themoldings with an external mold release agent, for example a productbased on wax, soaps or oil or a silicone oil. This method is not onlytime-consuming and costly, but can also, particularly in the case ofsilicone-containing mold release agents, lead to considerable problemsin applying a surface coating.

To improve the self-releasing properties in the production of PUmoldings, particularly PU-polyurea moldings by the RIM technique,“internal” mold release agents have been developed.

According to EP-A-0 153 639 (U.S. Pat. No. 4,581,387), PU-polyureamoldings are produced by the RIM technique using internal mold releaseagents comprising carboxylic esters and/or carboxamides which areprepared by esterification or amidation of a mixture of montanic acidand at least one aliphatic carboxylic acid having at least 10 carbonatoms with at least difunctional alkanol-amines, polyols and/orpolyamines having molecular weights of from 60 to 400.

According to U.S. Pat. No. 4,519,965, internal mold release agents usedin reaction injection molding are mixtures of at least one zinccarboxylate having from 8 to 24 carbon atoms in the carboxyl radical andnitrogen-containing polymers which react with isocyanate groups toimprove the compatibility of the zinc carboxylate with the formativecomponents used for polyurethane-polyurea production.

EP-A-0 255 905 (U.S. Pat. No. 4,766,172) describes a mold releasecomposition and a process for producing elastic moldings, which moldrelease composition comprises a solution which is liquid at roomtemperature of a zinc salt of a higher aliphatic carboxylic acid inselected tertiary amino compounds of the formulaR¹R²N(CH₂)_(m)NR(CH₂)_(n)NR³R⁴.

According to DE-A-36 31 842 (U.S. Pat. No. 4,764,537), internal moldrelease agents for producing moldings by the polyisocyanate polyadditionprocess comprise at least one ketimine, aldimine, enamine and/or acyclic Schiff base, at least one metal salt of an organic carboxylicacid having from 8 to 24 carbon atoms and at least one organiccarboxylic acid, organic sulfonic acid, mineral acid or amidosulfonicacid. These mold release compositions display excellent releaseproperties in essentially compact moldings containing urethane and ureagroups and rigid polyurethane integral foams produced by the RIMtechnique.

However, disadvantages are that the moldings containing urethane groupsand produced using chain extenders based on low molecular weightpolyhydric alcohols and/or polyoxyalkylene polyols cure relativelyslowly and have to be treated with 1,1,3-trichloro-ethane vapor toremove the grease before application of a surface coating.

To eliminate this disadvantage, elastic, essentially compactpolyurethane moldings as described in EP-B-0 262 378 and DE-A-39 04 810and flexible moldings containing urethane groups and having a compactsurface zone and a cellular core as described in DE-A-39 04 812 areproduced using an internal mold release agent comprising a mixture of atleast one organic amine and at least one metal salt of stearic acid or amixture of at least one organic amine, at least one ketimine and atleast one metal salt of stearic acid in combination with at least oneorganic monocarboxylic and/or dicarboxylic acid or anhydride. Anadvantage of these processes is that the PU moldings produced require nosurface treatment with 1,1,3-trichloroethane vapor. However, it has thedisadvantage that large-area moldings, in particular those havingcomplicated three-dimensional shapes, can be produced only withdifficulty since the flow path of the reaction mixture is relativelyshort so that large-volume molds, particularly those having thin hollowspaces and narrow flow channels, are frequently filled onlyinsufficiently or not at all at certain points.

Selection of the optimum mold release agent in each case usuallyrequires not only a knowledge of the starting materials in the PU orPU-polyurea formulation, eg. the presence or absence of zinc stearate,sterically hindered aromatic diamines, polyoxyalkylene-polyamines,blowing agents, etc., but also the type of mold material, the nature ofits surface and the mold geometry and also the arrangement of thefilling openings. In most cases, the selection of the best mold releaseagent requires experimental optimization.

Further external and/or internal mold release agents for producing PUfoams are described, for example, in EP 0 533 018 B1, DE-A-19 53 637,DE-A-21 21 670, DE-B-23 07 589, DE-A-23 56 692, DE-A-23 63 452, DE-A-2404 310, DE-A-24 27 273, DE-A-24 31 968 and for producing PU moldingshaving a thickness in the range from 0.8 to 1.4 g/cm³ in EP-A-0 265 781.Despite these many known methods, the problems involved in theself-release of PU or PU-polyurea moldings have not been able to besolved conclusively. The release action of the mold release agents usedis frequently insufficient and/or the polyol component containing themold release agents does not have a satisfactory shelf life.

Alkylsuccinic and alkenylsuccinic acids have already been used forproducing polyisocyanate polyaddition products. According to EP-A-666880 (WO 95/06673), alkali metal and alkaline earth metal salts ofalkylsuccinic and alkenylsuccinic acids are suitable as catalysts forproducing polyurethanes and/or polyureas, in particular foams comprisingsuch polyaddition products, since the acids are able to advantageouslyinfluence the cell structure of the foams.

It is an object of the present invention to develop internal moldrelease agents which have a broad range of applications and are suitablefor producing both compact and cellular moldings comprisingpolyisocyanate polyaddition products, for example polyaddition productscontaining urethane and/or urea and/or isocyanurate groups. The polyolcomponents (A components) containing the mold release agents should bestable on storage and be able to be processed by an economical,environmentally friendly process to give compact or cellular, preferablylarge-area and/or large-volume, moldings which may contain reinforcingmaterial or moldings having an essentially compact surface zone and acellular core, viz. integral foams.

If the moldings obtained are to have a surface coating applied, itshould be possible to omit, preferably completely, a pretreatment withorganic solvents, in particular halogen-containing solvents.

We have found that this object is achieved by the use of diesters and/ormonoesters of alkylsuccinic and/or alkenylsuccinic acids as internalmold release agents for producing the moldings comprising polyisocyanatepolyaddition products.

The present invention accordingly provides a process for producingself-releasing, compact or cellular moldings which comprisepolyisocyanate polyaddition products and may contain reinforcingmaterial by reacting

a) organic and/or modified organic polyisocyanates with

b) at least one compound containing at least two reactive hydrogen atomsand having a molecular weight of from 62 to 10,000 and, if desired,

c) chain extenders and/or crosslinkers in the presence of

d) internal mold release agents and in the presence or absence of

e) catalysts,

f) blowing agents,

g) reinforcing material and

h) auxiliaries

in an open or closed mold, with or without compaction, wherein theinternal mold release agents used are diesters and/or monoesters ofalkylsuccinic acids and/or diesters and/or monoesters of alkenylsuccinicacids.

The present invention further provides for the use of the alkylsuccinicdiesters or monoesters and alkenylsuccinic diesters and/or monoesters,preferably selected from the group consisting of alkylsuccinic andalkenylsuccinic diesters and monoesters, poly(alkylsuccinic) andpoly(alkenylsuccinic) polyesters or mixtures of alkylsuccinic diestersand/or monoesters and/or alkenylsuccinic diesters and/or monoestersand/or alkylsuccinamides and/or alkylsuccinimides and/oralkenylsuccinamides and/or alkenylsuccinimides, as internal mold releaseagents for producing moldings comprising polyisocyanate polyadditionproducts.

The internal mold release agents which can be used according to thepresent invention are free of metal ions, readily miscible with theother constituents of the polyol component (A component) and, owing tothe good solubility, have a very good shelf life. Certain internal moldrelease agents of the present invention are also soluble in the Bcomponent. Materials added to the B component are preferably ones which,as discussed later, are starting substances for the mold release agentsof the present invention. The alkylsuccinic and in particularalkenylsuccinic diesters and/or monoesters display a considerablyimproved release action in the production of moldings, essentiallyregardless of the composition of the polyol component. Owing to thebroad range of uses of the individual PU systems, the novel mold releaseagents can be used equally well in producing compact or cellularmoldings which contain urethane and urea groups and possiblyisocyanurate groups and may contain reinforcing material or be free ofreinforcing material.

Regarding the formative components (a) to (h) for producing the compactor cellular polyisocyanate polyaddition products and in particularregarding the internal mold release agents (d) which can be usedaccording to the present invention and the starting materials for theirpreparation, the following may be said:

a) Suitable organic polyisocyanates are the aliphatic, cycloaliphatic,araliphatic and preferably aromatic polyfunctional isocyanates known perse.

Specific examples are: alkylene diisocyanates having from 4 to 12 carbonatoms in the alkylene radical, eg. dodecane 1,12-diisocyanate,2-ethyltetramethylene 1,4-diisocyanate, 2-methylpentamethylene1,5-diisocyanate, tetramethylene 1,4-diisocyanate and preferablyhexamethylene 1,6-diisocyanate; cycloaliphatic diisocyanates such ascyclohexane 1,3- and 1,4-diisocyanate and also any mixtures of theseisomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanato-methylcyclohexane(isophorone diisocyanate), hexahydrotolylene 2,4- and 2,6-diisocyanateand also the corresponding isomer mixtures, dicyclohexylmethane4,4′-2,2′- and 2,4′- diisocyanate and also the corresponding isomermixtures, araliphatic diisocyanates such as m-, p-xylylene diisocyanateand xylylene diisocyanate isomer mixtures and preferably aromaticdiisocyanates and polyisocyanates such as tolylene 2,4- and2,6-diisocyanate and the corresponding isomer mixtures, diphenylmethane4,4′-, 2,4′, and 2,2′-diisocyanate and the corresponding isomermixtures, mixtures of diphenylmethane 4,4′- and 2,4′-diisocyanates,polyphenylpolymethylene polyisocyanates, mixtures of diphenylmethane4,4′-, 2,4′- and 2,2′-diisocyanates and polyphenylpolymethylenepolyisocyanates (raw MDI), mixtures of raw MDI and tolylenediisocyanates, naphthylene 1,4- and 1,5-diisocyanate,3,3′-dimethylbiphenyl 4,4′-diisocyanate, 1,2-diphenylethane diisocyanateand phenylene diisocyanate. The organic diisocyanates andpolyisocyanates can be used individually or in the form of mixtures.

Use is frequently also made of modified polyfunctional isocyanates, ie.products which are obtained by chemical reaction of organicdiisocyanates and/or polyisocyanates. Examples which may be mentionedare diisocyanates and/or polyisocyanates containing ester, urea, biuret,allophanate, carbodiimide, isocyanurate, uretdione, uretonimine and/orurethane groups. Specific examples are: organic, preferably aromatic,polyisocyanates containing urethane groups and having NCO contents offrom 33.6 to 15% by weight, preferably from 31 to 21% by weight, basedon the total weight, diphenylmethane 4,4′-diisocyanate modified, forexample, with low molecular weight alkanediols, triols, dialkyleneglycols, trialkylene glycols or polyoxyalkylene glycols having molecularweights of up to 6000, modified diphenylmethane 4,4′- and2,4′-diisocyanate mixtures, or modified raw MDI or tolylene 2,4- or2,6-diisocyanate, with examples of dialkylene or polyoxyalkylene glycolswhich can be used individually or as mixtures being: diethylene glycol,dipropylene glycol, polyoxyethylene, polyoxypropylene andpolyoxypropylene-polyoxyethylene glycols, triols and/or tetrols. Alsosuitable are prepolymers containing NCO groups, having NCO contents offrom 14 to 1.5% by weight, preferably from 8 to 2.5% by weight, based onthe total weight, and prepared from the polyester polyols and/orpreferably polyether polyols described below and naphthylene 1,4- and1,5-diisocyanate, 3,3′-dimethylbiphenyl 4,4′-diisocyanate,1,2-diphenylethane diisocyanate, phenylene diisocyanate anddiphenylmethane 4,4′-diisocyanate, mixtures of diphenylmethane 2,4′- and4,4′-diisocyanate, tolylene 2,4- and/or 2,6-diisocyanates or raw MDI.Further modified polyisocyanates which have been found to be useful areliquid polyisocyanates containing carbodiimide groups and/orisocyanurate rings and having NCO contents of from 33.6 to 15% byweight, preferably from 31 to 21% by weight, based on the total weight,for example those based on diphenylmethane 4,4′-, 2,4′- and/or2,2′-diisocyanate and/or tolylene 2,4- and/or 2,6-diisocyanate.

If desired, the modified polyisocyanates can be mixed with one anotheror with unmodified organic polyisocyanates such as diphenylmethane 2,4′-and/or 4,4′-diisocyanate, raw MDI, tolylene 2,4- and/or2,6-diisocyanate.

Organic polyisocyanates which have been found to be particularly usefuland are preferably employed for producing cellular elastomers are:prepolymers containing NCO groups and having an NCO content of from 14to 9% by weight, particularly those based on polyether polyols orpolyester polyols and one or more diphenylmethane diisocyanate isomers,advantageously diphenylmethane 4,4′-diisocyanate and/or modified organicpolyisocyanates containing urethane groups and having an NCO content offrom 33.6 to 15% by weight, in particular those based on diphenylmethane4,4′-diisocyanate or diphenylmethane diisocyanate isomer mixtures; forproducing flexible polyurethane foams: mixtures of tolylene 2,4- and2,6-diisocyanates, mixtures of tolylene diisocyanates and raw MDI or, inparticular, mixtures of the abovementioned prepolymers based ondiphenylmethane diisocyanate isomers and raw MDI; and for producingrigid polyurethane or polyurethane-polyisocyanurate foams: raw MDI.

b) As compounds b) containing at least two reactive hydrogen atoms, useis advantageously made of those having a functionality of from 1 to 8,preferably from 2 to 6, and a molecular weight of from 500 to 9000.Compounds which have been found to be useful are, for example,polyetherpolyamines and/or preferably polyols selected from the groupconsisting of polyether polyols, polyester polyols, polythioetherpolyols, hydroxyl-containing polyester amides, hydroxyl-containingpolyacetals and hydroxyl-containing aliphatic polycarbonates or mixturesof at least two of the polyols mentioned. Preference is given to usingpolyester polyols and/or polyether polyols.

Suitable polyester polyols can be prepared, for example, from organicdicarboxylic acids having from 2 to 12 carbon atoms, preferablyaliphatic dicarboxylic acids having from 4 to 6 carbon atoms, andpolyhydric alcohols, preferably diols, having from 2 to 12 carbon atoms,preferably from 2 to 6 carbon atoms. Suitable dicarboxylic acids are,for example: succinic acid, glutaric acid, adipic acid, suberic acid,azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid,fumaric acid, phthalic acid, isophthalic acid and terephthalic acid. Thedicarboxylic acids can here be used either individually or in admixturewith one another. In place of the free dicarboxylic acids, it is alsopossible to use the corresponding dicarboxylic acid derivatives such asdicarboxylic monoesters and diesters of alcohols having from 1 to 4carbon atoms or dicarboxylic anhydrides. Preference is given to usingdicarboxylic acid mixtures of succinic, glutaric and adipic acid inweight ratios of, for example, 20-35:35-50:20-32, and in particularadipic acid. Examples of dihydric and polyhydric alcohols, in particularalkanediols and dialkylene glycols, are: ethanediol, diethylene glycol,1,2- or 1,3-propanediol, dipropylene glycol, 1,4-butanediol,1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, glycerol andtrimethylolpropane. Preference is given to using ethanediol, diethyleneglycol 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol or mixtures of atleast two of the diols mentioned, in particular mixtures of1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol. It is also possibleto use polyester polyols derived from lactones, eg. ε-caprolactone, orhydroxycarboxylic acids, eg. ω-hydroxycaproic acid.

To prepare the polyester polyols, the organic, for example aromatic andpreferably aliphatic polycarboxylic acids and/or derivatives andpolyhydric alcohols can be polycondensed in the absence of catalysts orpreferably in the presence of esterification catalysts, advantageouslyin an atmosphere of inert gases such as nitrogen, carbon monoxide,helium, argon, etc., in the melt at from 150 to 250° C., preferably from180 to 220° C., under atmospheric or reduced pressure to the desiredacid number which is advantageously less than 10, preferably less than2. According to a preferred embodiment, the esterification mixture ispolycondensed at the abovementioned temperatures to an acid number offrom 80 to 30, preferably from 40 to 30, under atmospheric pressure andsubsequently under a pressure of less than 500 mbar, preferably from 50to 150 mbar. Examples of suitable esterification catalysts are iron,cadmium, cobalt, lead, zinc, antimony, magnesium, titanium and tincatalysts in the form of metals, metal oxides or metal salts. However,the polycondensation can also be carried out in the liquid phase in thepresence of diluents and/or entrainers such as benzene, toluene, xyleneor chlorobenzene to azeotropically distill off the water ofcondensation.

To prepare the polyester polyols, the organic polycarboxylic acidsand/or derivatives and polyhydric alcohols are advantageouslypolycondensed in a molar ratio of 1:1-1.8, preferably 1:1.05 to 1.2.

To prepare low-fogging PU moldings, the polyester polyols areadvantageously subjected before use to a distillation at from 140 to280° C. under a reduced pressure of from 0.05 to 30 mbar, eg. athin-film distillation, to remove volatile constituents.

The polyester polyols obtained preferably have a functionality of from 1to 4, in particular from 2 to 3, and a molecular weight of from 500 to3000, preferably from 1200 to 3000 and in particular from 1800 to 2500.

However, polyols which are particularly preferably used are polyetherpolyols which are prepared by known methods, for example from one ormore alkylene oxides having from 2 to 4 carbon atoms in the alkyleneradical by anionic polymerization using alkali metal hydroxides such assodium or potassium hydroxide or alkali metal alkoxides such as sodiummethoxide, sodium or potassium ethoxide or potassium isopropoxide ascatalysts with addition of at least one initiator molecule containingfrom 2 to 8, preferably from 2 to 6, reactive hydrogen atoms in bondedform, or by cationic polymerization using Lewis acids such as antimonypenta-chloride, boron fluoride etherate, etc., or bleaching earth ascatalysts.

Suitable alkylene oxides are, for example, tetrahydrofuran,1,3-propylene oxide, 1,2- or 2,3-butylene oxide, styrene oxide andpreferably ethylene oxide and 1,2-propylene oxide. The alkylene oxidescan be used individually, alternately in succession or as mixtures.Suitable initiator molecules are, for example: water, organicdicarboxylic acids such as succinic acid, adipic acid, phthalic acid andterephthalic acid, aliphatic and aromatic, unalkylated, N-monoalkylated,N,N- and N,N′-dialkylated diamines having from 1 to 4 carbon atoms inthe alkyl radical, for example unalkylated, monoalkylated or dialkylatedethylenediamine, diethylene-triamine, triethylenetetramine,1,3-propylenediamine, 1,3- or 1,4-butylenediamine, 1,2-, 1,3-, 1,4-,1,5- and 1,6-hexamethylenediamine, phenylenediamines, 2,3-, 2,4, 3,4-and 2,6-tolylenediamine and 4,4′-, 2,4′- and2,2′-diamino-diphenylmethane, N,N-dimethylaminodipropylenetriamine,N,N-dimethylaminopropane-1,3-diamine.

Further suitable initiator molecules are: alkanolamines such asethanolamine, N-methylethanolamine and N-ethylethanolamine,dialkanolamines such as diethanolamine, N-methyldiethanolamine andN-ethyldiethanolamine and trialkanolamines such as triethanolamine, andammonia. Preference is given to using polyhydric, in particular dihydricand/or trihydric, alcohols such as ethanediol, 1,2- and 1,3-propanediol,diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol,glycerol, trimethylolpropane, pentaerythritol, sorbitol and sucrose.

The polyether polyols, preferably polyoxypropylene andpolyoxypropylene-polyoxyethylene polyols, have a functionality ofpreferably from 2 to 3 and in particular from 2 to 2.6 and molecularweights of from 1800 to 9000, preferably from 2000 to 6500 and inparticular from 2400 to 5200, for producing flexible moldings and afunctionality of preferably from 3 to 8, in particular from 3 to 6, andmolecular weights of from 500 to 2400, preferably from 600 to 1800 andin particular from 600 to 1500 for producing stiff, rigid moldings andsuitable polyoxytetramethylene glycols have a molecular weight of up toabout 3500.

Further suitable polyether polyols are polymer-modified polyetherpolyols, preferably graft polyether polyols, in particular those basedon styrene and/or acrylonitrile which are prepared by in situpolymerization of acrylonitrile, styrene or preferably mixtures ofstyrene and acrylonitrile, eg. in a weight ratio of from 90:10 to 10:90,preferably from 70:30 to 30:70, advantageously in the abovementionedpolyether polyols using methods similar to those written in the GermanPatents 11 11 394, 12 22 669 (U.S. Pat. Nos. 3,304,273, 3,383,351,3,523,093), 11 52 536 (GB 10 40 452) and 11 52 537 (GB 987 618), andalso polyether polyol dispersions which contain as dispersed phase,usually in an amount of from 1 to 50% by weight, preferably from 2 to25% by weight: eg. polyureas, polyhydrazides, polyurethanes containingbonded tert-amino groups and/or melamine and are described, for example,in EP-B-011 752 (U.S. Pat. No. 4,304,708), U.S. Pat. No. 4,374,209 andDE-A-32 31 497.

Like the polyester polyols, the polyether polyols can be usedindividually or in the form of mixtures. They can also be mixed with thegraft polyether polyols or polyester polyols or with thehydroxyl-containing polyester amides, polyacetals, polycarbonates and/orpolyetherpolyamines.

Suitable hydroxyl-containing polyacetals are, for example, the compoundswhich can be prepared from glycols such as diethylene glycol,triethylene glycol, 4,4′-dihydroxyethoxy-diphenyldimethylmethane orhexanediol and formaldehyde. Suitable polyacetals can also be preparedby polymerization of cyclic acetals.

Suitable hydroxyl-containing polycarbonates are those of the type knownper se which can be prepared, for example, by reacting diols such as1,3-propanediol, 1,4-butanediol and/or 1,6-hexanediol, diethyleneglycol, triethylene glycol or tetraethylene glycol with diarylcarbonates, eg. diphenyl carbonate, or phosgene.

The hydroxyl-containing polyesteramides include, for example, thepredominantly linear condensates obtained from polybasic, saturatedand/or unsaturated carboxylic acids or their anhydrides andpolyfunctional saturated and/or unsaturated aminoalcohols or mixtures ofpolyfunctional alcohols and aminoalcohols, and/or polyamines.

Suitable polyetherpolyamines can be prepared from the abovementionedpolyether polyols by known methods. Examples which may be mentioned arethe cyanoalkylation of polyoxyalkylene polyols and subsequenthydrogenation of the nitrile formed (U.S. Pat. No. 3,267,050) or thepartial or complete amination of polyoxyalkylene polyols using amines orammonia in the presence of hydrogen and catalysts (DE 12 15 373).

c) The polyisocyanate polyaddition products can be prepared with orwithout concomitant use of difunctional chain extenders and/ortrifunctional and higher-functional crosslinkers. However, the additionof chain extenders, crosslinkers or, if desired, mixtures thereof canprove to be advantageous for modifying the mechanical properties, eg.the hardness. To produce compact and cellular PU or PU-polyureaelastomers, thermoplastic polyurethanes and flexible PU foams, it isadvantageous to use chain extenders and possibly crosslinkers. Chainextenders and/or crosslinkers used are diols and/or triols havingmolecular weights of less than 500, preferably from 60 to 300. Suitablechain extenders/crosslinkers are, for example, dialkylene glycols andaliphatic, cycloaliphatic and/or araliphatic diols having from 2 to 14,preferably from 4 to 10, carbon atoms, eg. ethylene glycol,1,3-propanediol, 1,10-decanediol, o-, m-, p-dihydroxycyclohexane,diethylene glycol, dipropylene glycol and preferably 1,4-butanediol,1,6-hexanediol and bis(2-hydroxyethyl)hydroquinone, triols such as1,2,4- or 1,3,5-trihydroxycyclohexane, glycerol and trimethylolpropaneand low molecular weight hydroxyl-containing polyalkylene oxides basedon ethylene oxide and/or 1,2-propylene oxide and the abovementioneddiols and/or triols as initiator molecules.

To produce cellular polyurethane(PU)-polyurea elastomers, it is alsopossible to use secondary aromatic diamines, primary aromatic diamines,3,3′-dialkyl- and/or 3,3′,5,5′-tetra- and alkyl-substituteddiaminodiphenylmethanes as chain extenders or crosslinkers in place ofthe abovementioned diols and/or triols or in admixture with these.

Examples of secondary aromatic diamines are: N,N′-dialkyl-substitutedaromatic diamines which may, if desired, be substituted by alkylradicals on the aromatic ring and have from 1 to 20, preferably from 1to 4, carbon atoms in the N-alkyl radical, eg. N,N′-diethyl-,N,N′-di-sec-pentyl-, N,N′-di-sec-hexyl-, N,N′-di-sec-decyl-,N,N′-dicyclohexyl-p- or -m-phenylenediamine, N,N′-dimethyl-,N,N′-diethyl-, N,N′-diisopropyl-, N,N′-di-sec-butyl-,N,N′-dicyclohexyl-4,4′-diaminodiphenylmethane andN,N′-di-sec-butylbenzidine.

Aromatic diamines which are advantageously used are those which have atleast one alkyl substituent in the ortho position relative to the aminogroups, are liquid at room temperature and are miscible with thecomponent (b), in particular the polyether polyols. Aromatic diamineswhich have been found to be useful are, for example, alkyl-substitutedmeta-phenylenediamines of the formulae

where R³ and R² are identical or different and are each a methyl, ethyl,propyl or isopropyl radical and R¹ is a linear or branched alkyl radicalhaving from 1 to 10, preferably from 4 to 6, carbon atoms.

Alkyl radicals R¹ which have been found to be particularly useful arethose in which the branched point is located on the C¹ carbon atom.Examples or radicals R¹ are the methyl, ethyl, isopropyl, 1-methyloctyl,2-ethyloctyl, 1-methylhexyl, 1,1-dimethylpentyl, 1,3,3-trimethylhexyl,1-ethylpentyl, 2-ethylpentyl and preferably the cyclohexyl,1-methyl-n-propyl, tert-butyl, 1-ethyl-n-propyl, 1-methy-n-butyl and1,1-dimethyl-n-propyl radical.

Examples of suitable alkyl-substituted n-phenylenediamines are:2,4-dimethyl-6-cyclohexyl-, 2-cyclohexyl-4,6-diethyl-,2-cyclohexyl-2,6-isopropyl-, 2,4-dimethyl-6-(1-ethyl-n-propyl)-,2,4-dimethyl-6-(1,1-dimethyl-n-propyl)-,2-(1-methyl-n-butyl)-4,6-dimethyl-phenylene-1,3-diamine. Preference isgiven to using 1-methyl-3,5-diethyl-2,4- or -2,6-phenylenediamine,2,4-dimethyl-6-tert-butyl-, 2,4-dimethyl-6-isooctyl- and2,4-dimethyl-6-cyclo-hexyl-phenylene-1,3-diamine.

Suitable 3,3′-di- and 3,3′,5,5′-tetra-n-alkyl-substituted4,4′-diaminodiphenylmethanes are, for example, 3,3′-dimethyl-,3,3′,5,5′-tetramethyl-, 3,3′-diethyl-, 3,3′,5,5′-tetraethyl-,3,3′-di-n-propyl and3,3′,5,5′-tetra-n-propyl-4,4′-diaminodiphenylmethane.

Preference is given to diaminodiphenylmethanes of the formula

where R⁴, R⁵, R⁶ and R⁷ are identical or different and are each amethyl, ethyl, propyl, isopropyl, sec-butyl or tert-butyl radical, butwhere at least one of the radicals has to be an isopropyl or sec-butylradical. The 4,4′-diaminodiphenylmethanes can also be used in admixturewith isomers of the formulae

where R⁴, R⁵, R⁶ and R⁷ are as defined above.

Preference is given to using 3,5-dimethyl-3′,5′-diisopropyl- and3,3′,5,5′-tetraisopropyl-4,4′-diaminodiphenylmethane. Thediaminodiphenylmethanes can be used individually or in the form ofmixtures.

The chain extenders and/or crosslinkers (c) mentioned can be usedindividually or as mixtures of similar or different types of compounds.

If chain extenders, crosslinkers or mixtures thereof are employed, theyare advantageously used in amounts of from 2 to 60% by weight,preferably from 8 to 50% by weight and in particular from 10 to 40% byweight, based on the weight of the component (b).

(d) According to the present invention, internal mold release agents (d)used are alkylsuccinic diesters, alkenylsuccinic diesters, alkylsuccinicmonoesters and alkenylsuccinic monoesters or mixtures of these diestersand monoesters. The alkyl or preferably alkenyl groups can be linear orpreferably branched and advantageously have a mean molecular weightM_(n) (number average) of from 250 to 3000, preferably from 800 to 2300and in particular from 900 to 1400. The alkyl groups preferably comprisepolyethylene, polyisopropylene and polyisobutylene radicals and thealkenyl groups preferably comprise polyphenyl, polyisopropenyl and inparticular polyisobutenyl radicals.

The alkylsuccinic or alkenylsuccinic diesters or monoesters can beprepared by known methods, for example by reacting alkylsuccinic oralkenylsuccinic acid and/or the corresponding alkylsuccinic oralkenylsuccinic acid derivatives such as monochlorides and/ordichlorides and in particular anhydrides with primary and/or secondaryorganic, preferably aliphatic and/or cycloaliphatic monoalcohols and/orpolyalcohols. According to a preferred embodiment, the alkylsuccinic oralkenylsuccinic esters are prepared by reacting the alkylsuccinic oralkenylsuccinic anhydrides with primary and/or secondary, aliphaticand/or cycloaliphatic monools and/or polyols, if desired in admixturewith alkylsuccinamides and/or alkylsuccinimides and/oralkenylsuccinamides and/or alkenylsuccinimides.

As formative components for preparing the alkylsuccinic oralkenylsuccinic diesters or monoesters, preference is given to usingalkylsuccinic or alkenylsuccinic anhydrides as are described, forexample, in EP-A-666 880 (WO 94 00 937), DE-A-28 08 105 (U.S. Pat. No.4,234,435) EP-A-0 632 071 (U.S. Pat. No. 5,420,207) or EP-A-0 629 638.However, other suitable starting materials are alkylsuccinic oralkenylsuccinic acids and acid derivatives, eg. monohalides and/ordihalides and preferably anhydrides of alkylsuccinic or alkenylsuccinicacids, as are described, for example, in EP-A-0 457 599, homopolymers ofpolyalkenyl-substituted succinic acid or derivatives, preferablyanhydrides, copolymers of the abovementioned polyalkenyl-substitutedsuccinic acids and/or succinic acid derivatives and olefinicallyunsaturated monomers having from 2 to 30 carbon atoms and copolymers ofmaleic anhydride, polyisoalkenes, preferably polyisopropene and inparticular polyisobutene, and olefinically unsaturated monomers havingfrom 2 to 30 carbon atoms, preferably from 18 to 24 carbon atoms.Suitable polymeric substances as formative components for the moldrelease agents of the present invention are also described in WO90/03359. The substances described there can be reacted as in WO90/03359 to give imides, amides, diesters or monoesters.

The preparation and work-up of suitable polyisobutylene is described,for example, in EP-A-628 575.

DE-A-28 08 105 (U.S. Pat. No. 4,234,435), the complete contents of whichare incorporated by references into the present description, describesthe starting components used for the preparation of the internal moldrelease agents used according to the present invention and also thepreparation and the after-treatment of the compounds which can be usedas internal mold release agents and also their suitability as additivesfor mineral lubricating oils.

A further group of succinic acid derivatives which can be converted intothe internal mold release agents which can be used according to thepresent invention is described in WO 95/07944. These are copolymerscomprising

a) from 20 to 60 mol % of maleic acid or maleic anhydride,

b) from 10 to 70 mol % of at least one oligomer of propane or a branched1-olefin having from 4 to 10 carbon atoms, having a mean molecularweight M_(w) of from 300 to 5000, and

c) from 1 to 50 mol % of at least one monoethylenically unsaturatedcompound which can be copolymerized with the monomers a) and b).

Monomers c) used are

monoethylenically unsaturated C₃-C₁₀-monocarboxylic acids

linear 1-olefins having from 2 to 40 carbon atoms

vinyl and alkyl allyl ethers having from 1 to 40 carbon atoms in thealkyl radical.

In principle, it is also possible to replace maleic acid and maleicanhydride either partially or completely by other olefinicallyunsaturated carboxylic acids. However, owing to their betteravailability and better processibility, use is usually made of maleicacid and/or maleic anhydride.

Suitable alcohols for preparing the internal mold release agents usedaccording to the present invention are accordingly those of the formula(hereinafter referred to as component A)

R³OH)_(m)(X)

where R³ is a monovalent or polyvalent organic radical having thestructure Y

which is bonded to the OH groups via C—O bonds, where the carbon atom isnot a constituent of a carbonyl group and m is an integer from 1 toabout 16, preferably from 2 to 6. The alcohols can be aliphatic,cycloaliphatic, aromatic or heterocyclic, eg. aliphatically substitutedheterocyclic, cycloaliphatically substituted aromatic,cycloaliphatically substituted heterocyclic, heterocyclicallysubstituted aliphatic, heterocyclically substituted cycloaliphatic andheterocyclically substituted aromatic alcohols. With the exception ofthe polyoxyalkylene alcohols, the monohydric and polyhydric alcohols ofthe formula X usually contain not more than about 40 carbon atoms.Polyhydric alcohols are preferred since the diesters and/or monoestersof the present invention derived therefrom have extraordinarily goodrelease properties. Examples of polyoxyalkylene alcohols which aresuitable as building blocks for the mold release agents of the presentinvention are polyoxyalkylene alcohol demulsifiers for aqueousemulsions. For the purpose of the present invention, “demulsifiers” foraqueous emulsions are polyoxyalkylene alcohols which prevent or retardthe formation of aqueous emulsions or break aqueous emulsions; “aqueousemulsions” are oil-in-water or water-in-oil emulsions. Numerouscommercial polyoxyalkylene alcohol demulsifiers can be used as A). Theseinclude the reaction product of various organic amines, carboxamides andquaternary ammonium salts with ethylene oxide. Such polyethoxylatedamines, amides and quaternary salts, ethylene oxide condensates ofN-alkylalkylenediamines or tertiary amines are the ethylene oxidecondensates of primary fatty acid amines; ethylene oxide condensates offatty acid amides; polyethoxylated quaternary ammonium salts, eg.quaternary ammonium chlorides are commercial products.

Preferred demulsifiers as component A are liquid polyoxyalkylenealcohols and their derivatives. Suitable derivatives are, for example,hydrocarbyl ethers and carboxylic esters which are obtained by reactingthe alcohols with various carboxylic acids. Specific hydrocarbylradicals are, for example, alkyl, cycloalkyl, alkylaryl, aralkyl, andalkylarylalkyl radicals having up to about 40 carbon atoms, for examplemethyl, butyl, dodecyl, tolyl, phenyl, naphthyl, dodecylphenyl,p-octylphenylethyl and cyclohexyl groups. The ester derivatives can beprepared using, for example, monocarboxylic and polycarboxylic acidssuch as acetic acid, valeric acid, lauric acid, stearic acid and oleicacid, and polyols or liquid triols derived from ethylene oxide andpropylene oxide and having an average molecular weight of from 4000 to5000 as well as dodecylphenyl or nonylphenyl polyethylene glycol ethersand polyalkylene glycols and various derivatives which are commercialproducts.

Further products which are useful as component A are compounds which arederived from the above and have, on average, at least one free alcoholichydroxyl group per polyoxyalkylene molecule. In the case of thesedemulsifiers, a hydroxyl group is designated as alcoholic when it isbound to a carbon atom which is not a constituent of an aromatic ring.The preferred polyoxyalkylene polyols as component A include polyolswhich have been prepared as block polymers. For this purpose, ahydroxy-substituted compound R⁴-(OH)_(q) (where q is from 1 to 10 and R⁴is, for example, the radical of a monohydric or polyhydric alcohol or amonohydric or polyhydricphenol or naphthol) is reacted with an alkyleneoxide

(where R⁵ is hydrogen or a lower alkyl radical having up to 4 carbonatoms, R⁶ is hydrogen or is as defined for R⁵, with the proviso that thealkylene oxide contains not more than 10 carbon atoms) to form ahydrophobic base compound. This compound is then reacted with ethyleneoxide to form a hydrophilic part, resulting in a molecule havinghydrophobic and hydrophilic regions. The preparation of polyols havinghydrophilic and hydrophobic regions is known. Depending on the systemformulation of the polyurethane A component, targeted use is made ofpolyols which are converted as A) into mold release agents which, ifdesired, have a relatively high proportion of hydrophobic regions.However, it can also be advantageous to increase the hydrophilicproportion.

Examples of compounds of the formula R³—OH)_(m) are aliphatic polyolssuch as alkylene glycols and alkane polyols, eg. ethylene glycol,propylene glycol, trimethylene glycol, triethylene glycol,1,6-hexanediol, glycerol, pentaerythritol, dipentaerythritol,erythritol, sorbitol, sorbitan, xylose, dextrose, fructose, glucose,lactose, mannitol, sugar acids, xylitol, dextrins, dextrans, castor oil,malic acid, glyceric acid, tetracosanol, glyceraldehyde, tartaric acid,glucuronic acid, arabinose, fructose, sorbose, cetyl alcohol, lanolinalcohol, and also aromatic hydroxy compounds such as alkylatedmonohydric and polyhydric phenols and naphthols, eg. cresols,heptylphenols, dioctylphenols, resorcinol, pyrogallol. Further suitablepolyoxyalkylene polyols as component A) are those having from 2 to 4hydroxyl groups and molecules which consist essentially of hydrophobicparts containing

(where R⁵ is a lower alkyl radical having up to 3 carbon atoms) andhydrophilic parts containing —CH₂—CH₂—O— groups. Such polyols can beprepared by first reacting a compound of the formula R³OH)_(m) (where_(m) is from 2 to 6) with a terminal alkylene oxide of the formula

and then reacting the product with ethylene oxide. Examples ofR³OH)_(m) are: TMP (trimethylolpropane), TME (trimethylol-ethane),ethylene glycol, trimethylene glycol, tetramethylene glycol,tri-(β-hydroxypropyl)amine, 1,4-(2-hydroxyethyl)cyclohexane,N,N,N′,N′-tetrakis-(2-hydroxypropyl)ethylenediamine,N,N,N′,N′-tetrakis-(2-hydroxyethyl)ethylenediamine,tri-(β-hydroxyethyl)amine, N,N-dimethylaminopropanamine-1,3,N,N-dimethylamino-dipropylenetriamine, naphthol, alkylated naphthols,resorcinol. To be suitable as component A) for preparing the internalmold release agents, the polyoxyalkylene alcohols should have a meanmolecular weight of from about 500 to 10,000, preferably from about 200to 7000. The oxyethylene groups (—CH₂—CH₂—O—) normally make up fromabout 5 to 40% of the total average molecular weight.

The polyols mentioned are very useful as component A) for preparing theinternal mold release agents of the present invention. The polyolsmentioned can be reacted with inorganic acids such as boric acid,o-phosphoric acid, sulfuric acid, organic sulfonic acid, amidosulfonicacid or lower monocarboxylic and/or polycarboxylic acids and/or theirpartial esters, eg. phosphocarboxylic acids, formic acid, acetic acid,maleic acid, maleic monoesters, lactic acid or citric acid, or withfatty acids such as those derived from soybean oil, olive oil, sunfloweroil, linseed oil, resin oil, pine oil, lanolin, tall oil, fish oil,rapeseed oil and palm oil or ricinoleic acid, but in particular oleicacid, (iso)stearic acid, montanic acids, rosin acids,phenyl-alkylcarboxylic acids or phthalic acid or maleic monoesters oflong-chain fatty alcohols, with the proviso that one OH group remainsfree. In general, no esterification takes place in the case of theabove-described basic polyoxyalkylene polyols but rather a salt isformed with the acids mentioned. It has been found to be advantageous touse not the stoichiometric amount but rather a deficiency of the acids,in particular the fatty acids mentioned. Both the partial esters and thesalts are very useful as component A for preparing the mold releaseagents of the present invention.

Polyoxyalkylene polyols having a mean molecular weight of from about2500 to 6000 in which from 10 to 20% by weight of the molecule is madeup by the oxyethylene groups give monoesters having particularly goodproperties as component A for preparing the internal mold releaseagents.

Examples of such polyoxyalkylene polyols are

where x,y and z are integers greater than 1 so that the —CH₂—CH₂O—groups make up from about 10 to 15% by weight of the total molecularweight as glycols, with the average molecular weight of the polyolsbeing from about 2500 to 4500. This type of polyol is prepared byreacting propylene glycol first with propylene oxide and then withethylene oxide. The corresponding monoesters of these polyols areprepared using the abovementioned fatty acids.

Another group of preferred polyoxyalkylene alcohols as precursor A) arethe liquid polyols of the following structure:

They are described in U.S. Pat. No. 2,979,528. These polyols can beprepared by reacting an alkylenediamine such as ethylenediamine,propylenediamine or hexamethylenediamine with propylene oxide andsubsequently with ethylene oxide. The molecular weight is up to 10000.

A further polyether which is useful as component A) is a triol having amean molecular weight of from about 4000 to 5000 and derived frompropylene oxide and ethylene oxide, where the oxyethylene groups make upabout 18% by weight of the triol. The triols are prepared by reactingglycerol, TME or TMP with propylene oxide to form a hydrophobic part andsubsequently preparing the hydrophilic parts using ethylene oxide.

Further suitable polyethers A) are alkylene glycols and polyoxyalkylenealcohols such as polyoxyethylene alcohols, polyoxypropylene alcohols andpolyoxybutylene alcohols. These polyglycols can contain up to about 150oxyalkylene units, with the alkylene radical containing from 2 to 8carbon atoms. These polyoxyalkylene alcohols are generally dihydricalcohols, ie. each molecule has two hydroxyl groups as end groups. Forthese polyols to be suitable as A), they have to contain at least onesuch hydroxyl group. The remaining hydroxyl groups can be reacted with amonobasic, aliphatic or aromatic carboxylic acid having up to about 30carbon atoms, for example formic acid, acetic acid, propionic acid,butyric acid, valeric acid, n-caproic acid, caprylic acid, capric acid,lauric acid, palmitic acid, stearic acid, sugar acids such as lacticacid or citric acid or tartaric acid as well as benzoic acid, inparticular fatty acids, eg. those derived from soybean oil, olive oil,sunflower oil, linseed oil, resin oil, pine oil, lanolin, tall oil, fishoil, rapeseed oil and palm oil, ricinoleic acid, linoleic acid,linolenic acid, in particular oleic acid, montanic acids, rosin acids,phthalic acid or maleic monoesters of long-chain fatty alcohols, withthe proviso that one OH group remains free. When using polyoxyethyleneglycols which have a hydrophilic character, the abovementioned fattyacids have been found to be particularly useful as hydrophilic acids.

Examples which may be mentioned are PEG-400 monostearate, PEG-400monooleate and PEG-150 monolaurate, where PEG is a polyoxyethyleneglycol. The numbers indicate the mean molecular weight.

Products of the type described are commercial products. Further productsare POE (20) sorbitan monolaurate, POE (20) sorbitan monooleate, POE(20) sorbitan trioleate, POE (5) sorbitan trioleate and POE (20)lanolate. These products too are commercial products. POE represents thepolyoxyethylene radical and POE (20) denotes 20 ethylene oxide units.The number in brackets is the number of ethylene oxide units. It isimportant that at least one hydroxyl group is present in the moleculebefore the products are reacted with polyisobutylenesuccinic anhydride.Further examples are POE (5) lanolate, POE (20) lanolate. Also suitableare the monoesters of maleic acid with fatty alcohols. Polyoxypropyleneglycols which have an average molecular weight of from 600 to 4500 aresuitable for preparing monoesters. Preference is given to usingcarboxylic acids having up to 20 carbon atoms. Also suitable are sugaracids such as lactic acid, citric acid, boric acid, phosphoric acid,maleic monoesters of alkyl-substituted alkylphenols, which are reactedwith up to 25 mol of ethylene oxide. Also useful are the monoesters ofmaleic acid with polyoxyethylene glycols. The polyhydric alcoholsmentioned are likewise suitable as A). They preferably contain from 2 to10 hydroxyl groups. Examples are ethylene glycol, diethylene glycol,1,2-propanediol, triethylene glycol, tetraethylene glycol, dipropyleneglycol, tripropylene glycol, dibutylene glycol, tributylene glycol andother alkylene glycols and polyoxyethylene glycols in which the alkylradicals contain from 2 to about 8 carbon atoms.

Examples which may be mentioned are propylene glycol monolaurate,propylene glycol monoricinoleate, propylene glycol monostearate,ethylene glycol monostearate, diethylene glycol monolaurate.

The monoethers of these alkylene glycols and polyalkylene glycols arelikewise suitable as A). Examples are the monoarylene ethers, monoalkylethers and monoaralkyl ethers of these alkylene glycols andpolyoxyalkylene glycols. This group has the formula

where R_(c) is an aryl radical, eg. a phenyl, lower alkoxyphenyl orlower alkylphenyl group, a lower alkyl radical, eg. an ethyl, propyl,tert-butyl or phenyl group, or an aralkyl radical, eg. a benzyl,phenylethyl, phenylpropyl or p-ethylphenylethyl group, p is from 0 toabout 150 and R_(A) and R_(B) are lower alkylene radicals having from 2to about 3, preferably from 2 to 4, carbon atoms. Polyoxyalkyleneglycols in which the alkylene radicals are ethylene or propylene groupsand p is at least 2, and also their monoethers, are preferred. Furthersuitable monohydric and polyhydric alcohols (A) are aromatic monohydroxyand polyhydroxy compounds. Monohydric and polyhydric phenols andnaphthols are preferred aromatic hydroxy compounds. The aromatic hydroxycompounds can contain not only the hydroxy substituents but also furthersubstituents such as halogen atoms or alkyl, alkenyl, alkoxy,alkylmercapto or nitro groups. The aromatic hydroxy compounds usuallycontain from 1 to 4 hydroxyl groups. Specific examples of aromatichydroxy compounds are: phenol, p-chlorophenol, p-nitrophenol,β-naphthol, α-naphthol, cresoles, resorcinol, catechol, carvacrol,thymol, eugenol, p,p′-dihydroxybiphenyl, hydroquinone, pyrogallol,phloroglucinol, hexylresorcinol, orcinol, guajacol, 2-chlorophenol,2,4-dibutylphenol, (propene tetramer)-substituted phenol,didodecylphenol, 4,4′-methylene-bismethylene-bisphenol,α-decyl-β-naphthol, polyisobutenyl(molecular weight about1000)-substituted phenol, the condensation product of heptylphenol and0.5 mol of formaldehyde, the condensation product of octylphenol andacetone, di(hydroxyphenyl) oxide, di(hydroxyphenyl) sulfide,di(hydroxyphenyl) disulfide and 4-cyclohexylphenol. Particularpreference is given to phenol and phenols substituted by aliphatichydrocarbon radicals, eg. alkylated phenols having up to three aliphatichydrocarbon substituents. Each of the aliphatic hydrocarbon substituentscan contain 100 or more carbon atoms, but usually contains from 1 to 30carbon atoms. Alkyl and alkenyl radicals are preferred aliphatichydrocarbon substituents.

Further specific alcohols as component A are monohydric alcohols such asmethanol, ethanol, isopropanol, isooctanol, dodecanol, cyclohexanol,cyclopentanol, behenyl alcohol, hexatriacontanol, neopentyl alcohol,isobutanol, benzyl alcohol, β-thenyl alcohol, 2-methylcyclohexanol,β-chlorohexanol, ethylene glycol monomethyl ether, ethylene glycolmonobutyl ether, diethylene glycol monopropyl ether, triethylene glycolmonododecyl ether, ethylene glycol monostearate, diethylene glycolmonostearate, sec-pentyl alcohol, tert-butanol, σ-bromododecanol,glyceryl dioleate, lanolin alcohol, cholesterol, POE (5) lanolinalcohol, (POE) (10-40) lanolin alcohol, allyl alcohol, cetyl alcohol,cinnamyl alcohol, 1-cyclohexan-3-ol and oleyl alcohol. Also suitable arefatty alcohol ethers such as polyoxypropylene (10) cetyl alcohol,polyoxypropylene (20) cetyl alcohol, polyoxypropylene (15) stearylalcohol. Although the alcohols are in principle suitable as component A,it is of course also possible to use the abovementioned etherderivatives prepared by reacting, in particular, the fatty alcohols withethylene oxide. Such substances can also be obtained by reacting higherfatty acids with ethylene oxide. Examples which may be mentioned are POE(5) oleic acid or POE (20) lanolin fatty acid.

Other specific alcohols A) are ether alcohols and amino alcohols, eg.oxyalkylene-, oxyarylene-, aminoalkylene- and aminoarylene-substitutedalcohols having one or more oxyalkylene, aminoalkylene oraminoarylene-oxyarylene radicals. Examples of such alcohols are themonoalkyl and dialkyl ethers of ethylene glycol and diethylene glycol,phenoxyethanol, heptylphenyl-(oxypropylene)₆-OH,octyl-(oxyethylene)₃₀-OH, phenyl-(oxyethylene) ₃₀-OH,phenyl-(oxyoctylene)₂-OH, mono(heptylphenyloxypropylene)-substitutedglycerol, poly styrene oxide), aminoethanol, 3-aminoethylpentanol,di(hydroxyethyl)amino-p-aminophenol, tri(hydroxypropyl)amine,N-hydroxyethylethylenediamine andN,N,N′,N′-tetrahydroxytrimethylenediamine, tri(hydroxyethyl)amine,N,N,N′,N′-tetrakis(2-hydroxyethyl)-ethylenediamine andN,N,N′,N′-tetrakis(2-hydroxypropyl)-ethylenediamine and also theoxyalkylene derivatives thereof and the reaction product ofethylenediamine with 4 mol of propylene oxide. These products can alsobe reacted with ethylene oxide and/or propylene oxide. They can also bepartially esterified with monocarboxylic acids.

Further polyhydric alcohols which can be used as A are glycerol,glyceryl monooleate, glyceryl monostearate, glycerol monomethyl ether,pentaerythritol, n-butyl 9,10-dihydroxystearate, methyl9,10-dihydroxystearate 1,2-butanediol, 2,3-hexanediol, 2,4-hexanediol,pinacol, erythritol, arabitol, sorbitol, sorbitan, 1,2-cyclohexanediol,xylene glycol, carbohydrates such as sugar, starch, celluloses, etc.Examples of carbohydrates are glucose, fructose, sucrose, xylose,dextrose, lactose, mannitol, xylitol, rhamnose, dulcitol, glyceraldehydeand galacturonic acid.

Polyhydric alcohols having at least 3 hydroxyl groups of which some butnot all have been reacted with an aliphatic monocarboxylic acid havingfrom 8 to 30 carbon atoms, eg. with caprylic acid, oleic acid, stearicacid, linoleic acid, lauric acid, tall oil fatty acid, or ricinoleicacid, are particularly suitable as A). Further examples of suchpartially reacted polyhydric alcohols are sorbitol monooleate, sorbitoldistearate, glyceryl monooleate, glyceryl dioleate, erythritoldilaurate, sorbitan monooleate and sorbitan trioleate. The free OHgroups of the sorbitan products can be ethoxylated, eg. (POE) (20)sorbitan trioleate. Anhydrohexitols are prepared by dehydrating hexitols(eg. sorbitol, manitol and dulcitol), ie. by dehydrating hexahydric,aliphatic, straight-chain and saturated alcohols having 6 carbon atoms.Removal of a water molecule from hexitols gives the monoanhydrohexitols,also known as hexitans (eg. sorbitan) and removal of two molecules ofwater gives the dianhydrohexitols, also known as hexides (eg. sorbide orisosorbide).

As indicated above, sorbitan can be ethoxylated or esterified. Theethoxylated product can then also be esterified with a carboxylic acid,in particular a hydroxy acid. The esterification can be carried outusing sugar acids or hydroxy fatty acids such as ricinoleic acid and/orfatty acids from fish oil.

Sorbitan can be esterified using caproic acid, octanoic acid, capricacid, lauric acid, myristic acid, palmitic acid, stearic acid,eicosanoic acid, behenic acid, laurolinic acid, myristoleic acid,palmitoleic acid, oleic acid, ricinoleic acid, linoleic acid, linolenicacid, coconut oil fatty acid, lanolin fatty acid, tallow fatty acid andpalm oil fatty acid.

Preferred alcohols as component A) are polyhydric alcohols having up toabout 12 carbon atoms, in particular from 3 to 10 carbon atoms. Examplesof these are glycerol, erythritol, pentaerythritol, dipentaerythritol,gluconic acid, glyceraldehyde, glucose, arabinose, 1,7-heptanediol,1,2,3-hexanetriol, 1,2,4-hexanetriol, 1,2,5-hexanetriol,2,3,4-hexanetriol, 1,2,3-butanetriol, 1,2,4-butanetriol, quinic acid,2,2,6,6-tetrakis(hydroxymethyl)cyclohexanol, 1,10-decanediol anddigitoxose. A further group of preferred components A) are polyhydricalkanols having from 3 to 10 carbon atoms and at least 3 hydroxylgroups. Examples are: glycerol, erythritol, pentaerythritol, mannitol,sorbitol, sorbitan, 2-hydroxymethyl-2-methyl-1,3-propanediol(trimethylolethane), trimethylolpropane, 1,2,4-hexanetriol.

Amino alcohols which are suitable as A) generally contain only tertiaryamino groups. Amino alcohols containing primary, secondary and tertiaryamino groups are less suitable. Examples of compounds containingtertiary amino groups are triethanolamine, triisopropanolamine,N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenediamine,tri(2-hydroxyethyl)amine, N-(2-hydroxyethyl)morpholine,N-(2-hydroxyethyl)piperidine, N,N-di(2-hydroxyethyl)glycine and theirethers with aliphatic alcohols. Further suitable aminoalcohols may befound in the literature.

Further compounds which are useful as component A) are OH- containingvegetable and animal oils and fats, eg. castor oil and lard oil. Castoroil and its reaction products with ethylene oxide and/or propylene oxideare particularly suitable. Also suitable are compounds as are describedin EP 0 554 590. Further suitable compounds are alkylene oxide polymersand copolymers and their derivatives in which the terminal hydroxylgroups have been modified by, for example, esterification oretherification. Examples of such oils are the polymerization products ofethylene oxide or propylene oxide, the alkyl and aryl ethers of thesepolyoxyalkylene polymers (eg. polyisopropylene glycol methyl etherhaving a mean molecular weight of 1000, polyethylene glycol diphenylether having a molecular weight of 1000, polyethylene glycol diphenylether having a molecular weight of from 500 to 1000 or polypropyleneglycol diethyl ether having a molecular weight of from 1000 to 1500) ortheir monocarboxylic and polycarboxylic esters, eg. acetic esters, mixedC₃-C₈-fatty acid esters or C₁₃-oxo acid diesters or tetraethyleneglycol.

A further class is the esters of dicarboxylic acids (eg. phthalic acid,succinic acid, alkylsuccinic acids and alkenylsuccinic acids, maleicacid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipicacid, linoleic acid diamer, malonic acid, alkylmalonic acids oralkenylmalonic acids) with various alcohols (eg. butanol, hexanol,dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethyleneglycol monoether or propylene glycol). Specific examples of such estersare dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate,dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctylphthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyldiester of linoleic acid dimer and the ester prepared by reacting 1 molof sebacic acid with 2 mol of tetraethylene glycol and 2 mol of2-ethylcaproic acid.

Other esters which are suitable as synthetic oils are derived, forexample, from C₅-C₃₀- monocarboxylic acids and polyols or polyol etherssuch as neopentyl glycol, trimethylol propane, pentaerythritol,dipentaerythritol or tripentaerythritol.

Further esters are those based on aromatic or aliphatic dicarboxylicacids and alcohols, particularly in combination with oleic acid.

The mold release agents of the present invention are prepared by knownmethods. The reaction is generally carried out in such a way that fromabout 50 to 75% of the carboxyl groups are reacted. The internal moldrelease agents described are also suitable in combination with syntheticlubricants based on aromatic and aliphatic hydrocarbons or mineral oils.Preference is here given to reaction products of PIBSA and polyols.Suitable starting materials for the mold release agents of the presentinvention also include the compounds mentioned in claim 1b.

After the reaction, remaining acid groups can be deactivated by reactionwith groups reactive toward acid groups. Compounds suitable for thispurpose are listed in U.S. Pat. No. 4,234,435. Examples which may bementioned here are boron compounds, phosphorus compounds, epoxides andformaldehyde. It is also possible to deactivate the free carboxyl groupswith metal ions. Although the internal mold release agents of thepresent invention are preferably used in metal-free form and this bringsadvantages, for example a better surface of the moldings, there areindeed also applications in which the presence of metal ions ispossible.

The amount of internal mold release agents used is, depending on thegeometry and material of the molding, from 0.01 to 5 parts by weight,based on the component b) and can readily be determined by preliminaryexperiments. The internal mold release agents are usually added to thepolyol component. However, it can also be advantageous to add them tothe isocyanate component. It has been found to be useful to add theprecursors of the internal mold release agents (not acylated).

The internal mold release agents used according to the present inventionare very readily soluble in the formative components of polyurethanesand therefore have a good release action even in the case of moldingshaving a large area or complicated shapes.

(e) Catalysts (e) used for producing the polyisocyanate polyadditionproducts are, in particular, compounds which strongly accelerate thereaction of the hydroxyl-containing compounds of the component (b) and,if used, (c) with the organic, modified or unmodified polyisocyanates(a). Suitable catalysts are organic metal compounds, preferably organictin compounds such as tin(II) salts of organic carboxylic acids, eg.tin(II) diacetate, tin(II) dioctoate, tin(II) diethylhexanoate andtin(II) dilaurate, and the dialkyltin(IV) salts of organic carboxylicacids, eg. dibutyltin diacetate, dibutyltin dilaurate, dibutyltinmaleate and dioctyltin diacetate. Other compounds which have been foundto be well-suited are dialkyltin(IV) mercapto compounds such asbislauryltin(IV) dimercaptide and compounds of the formulaR₂Sn(SR′—O—CO—R′′)₂ or R₂Sn(SR′—CO—OR′′)₂, where R is an alkyl radicalhaving at least 8 carbon atoms, R′ is an alkyl radical having at least 2carbon atoms and R′′ is an alkyl radical having at least 4 carbon atoms.Examples of catalyst of this type, which are described, for example, inDD-A-218 668, are: dioctyltin bis(thioethylene glycol-2-ethylhexanoate),dioctyltin bis(thioethylene glycol laurate), dioctyltin bis(2-ethylhexylthiolatoacetate), dioctyltin bis(hexyl thiolatoacetate) and doctyltinbis(lauryl thiolatoacetate). Further catalysts which have been found tobe very useful are organotin compounds having tin-oxygen or tin-sulfurcompounds, as are described, for example, in DD-A-255 535. These havethe formula (R₃Sn)₂O, R₂SnS, (R₃Sn)₂S, R₂Sn(SR′)₂ or RSn(SR′)₃, where Rand R′0 are alkyl groups containing from 4 to 8 carbon atoms in the caseof R and from 4 to 12 carbon atoms in the case of R′ and R′ can also bea radical —R′′COOR′′ or —R′′OCOR′′′, where R′′ is an alkyl group havingfrom 1 to 6 carbon atoms and R′′′ is an alkylene group having from 4 to12 carbon atoms. Examples of such compounds are: bis(tributyltin) oxide,dibutyltin sulfide, dioctyltin sulfide, bis(tributyltin) sulfide,dibutyltin bis(2-ethylhexyl thioglycolate), dioctyltin bis(2-ethylhexylthioglycolate), octyltin tris(2-ethylhexyl thioglycolate), dioctyltinbis(thioethylene glycol 2-ethylhexanoate) and dibutyltinbis(thioethylene glycol laurate).

The organic metal compounds can be used as catalysts either individuallyor in the form of catalyst combinations. A combination which has beenfound to be extremely advantageous is that of di-n-octyltinbis(2-ethylhexyl thioglycolate) and mono-n-octyltin tris(2-ethylhexylthioglycolate), advantageously in a weight ratio of from 70:30 to 30:70or 94:6.

The organic metal compounds can also be used in combination withstrongly basic amines. Examples which may be mentioned are amidines suchas 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tertiary amines such astriethylamine, tributylamine, dimethylbenzylamine, N-methylmorpholine,N-ethylmorpholine, N-cyclohexylmorpholine,N,N,N′,N′-tetramethylethylenediamine,N,N,N′,N′-tetramethylbutanediamine,N,N,N′,N′-tetramethyldiaminodicyclohexylmethane,pentamethyldiethylenetriamine, bis(dimethylaminoethyl) ether,bis(dimethylaminopropyl)urea, dimethylpiperazine, 1,2-dimethylimidazol,1-azabicyclo[3.3.0]octane and preferably 1,4-diazabicyclo[2.2.2]octaneand alkanolamine compounds such as triethanolamine, triisopropanolamine,N-methyldiethanolamine and N-ethyldiethanolamine anddimethylethanolamine.

The further suitable catalysts, particularly when using an excess ofpolyisocyanate, are: tris(dialkylaminoalkyl)-s-hexahydrotriazines, inparticular tris(N,N-dimethylaminopropyl)-s-hexahydrotriazine,tetraalkylammonium hydroxides such as tetramethylammonium hydroxide,alkali metal hydroxides such as sodium hydroxide and alkali metalalkoxides such as sodium methoxide and potassium isopropoxide, alkalimetal formates and acetates such as potassium formate and potassiumacetate and also alkali metal salts of long-chain fatty acids havingfrom 10 to 20 carbon atoms and possibly lateral OH groups. Preference isgiven to using from 0.001 to 5% by weight, in particular from 0.05 to 2%by weight, of catalyst or catalyst combination, based on the weight ofthe component (b).

(f) As blowing agent (f) for producing the cellular PU or PU-polyureaelastomers and PU or PIR foams, preference is given to using water whichreacts with the organic, modified or unmodified polyisocyanates (a) toform carbon dioxide and amino groups which in turn react further withthe polyisocyanates (a) to form urea groups and can thereby influencethe mechanical properties of the cellular polyisocyanate polyadditionproducts.

To achieve the industrially customary densities, the water isadvantageously used in amounts of from 0.05 to 7% by weight, preferablyfrom 0.1 to 6% by weight and in particular from 2 to 4% by weight, basedon the weight of the formative components (a) to (c).

Other blowing agents (f) which can be used in place of water orpreferably in combination with water are low-boiling liquids whichvaporize under the action of the exothermic polyaddition reaction andadvantageously have a boiling point at atmospheric pressure in the rangefrom −40 to 80° C., preferably from 10 to 50° C., or gases.

The liquids of the abovementioned type and gases suitable as blowingagent can be selected, for example, from the group consisting of alkanessuch as propane, n- and iso-butane, n- and iso-pentane and preferablyindustrial pentane mixtures, cycloalkanes and cycloalkenes such ascyclobutane, cyclopentene, cyclohexene and preferably cyclopentaneand/or aged cyclohexane, dialkyl ethers such as dimethyl ether, methylethyl ether or diethyl ether, tert-butyl methyl ether, cycloalkyleneethers such as furan, ketones such as acetone and methyl ethyl ketone,carboxylic esters such as ethyl acetate, methyl formate and tert-butylethylene-acrylate, tertiary alcohols such as tert-butanol, carboxylicacids such as formic acid, acetic acid and propionic acid, fluoroalkaneswhich are degraded in the troposphere and therefore do not damage theozone layer, eg. trifluoromethane, difluoromethane, difluoroethane,tetrafluoroethane and heptafluoroethane, and gases such as nitrogen,carbon monoxide and noble gases such as helium, neon and krypton.

Other suitable blowing agents are salts which decompose thermally, eg.ammonium bicarbonate and/or ammonium carbamate, or compounds which formsuch salts in situ, eg. aqueous ammonia and/or amines and carbondioxide, and ammonium salts of organic carboxylic acids such as themonoammonium salts of malonic acid or boric acid.

The most advantageous amount of solid blowing agents, low-boilingliquids and gases, each of which can be used individually or in the formof mixtures, eg. as liquid mixtures or gas mixtures or as gas-liquidmixtures, depends on the density which is to be achieved and on theamount of water used. The amounts required can readily be determined bysimple experiments. Satisfactory results are usually given by amounts ofsolid of from 0.5 to 30 parts by weight, preferably from 2 to 15 partsby weight, amounts of liquid of from 1 to 15 parts by weight, preferablyfrom 3 to 12 parts by weight, and/or amounts of gas of from 0.01 to 80parts by weight, preferably from 10 to 35 parts by weight, in each casebased on the weight of the formative components (a), (b) and, if used,(c). The loading with gas, eg. air, carbon dioxide, nitrogen and/orhelium, can be carried out either via the relatively high molecularweight compounds (b) and, if used, low molecular weight chain extendersand/or crosslinkers (c), via the polyisocyanates (a) or via (a) and (b)and, if used, (c).

g) The compact or cellular moldings comprising polyisocyanatepolyaddition products produced by the process of the present inventioncan be provided with a covering layer, eg. of paint or varnish or adecorative material, and/or an insert as strengthening element and/or,in particular, a reinforcing material.

Suitable decorative materials are, for example, paper or cardboard, eachof which may be printed or colored, films made of TPU, PVC, polyvinylchloride-containing polymer mixtures, eg. PVC/ABS, PVC/PU,PVC/ABS/polyvinyl acetate, vinyl chloride-methacrylate-butadiene-styrenecopolymer or ethylene-vinyl acetate-vinyl chloride graft copolymer andtextiles or carpets.

Inserts which have been found to be useful are, for example, ones madeof metallic materials such as aluminum, copper, titanium, brass or steelsheet, or plastics such as TPU, polyamide, polycarbonate, polyalkyleneterephthalate, eg. polybutylene terephthalate, and polyolefinhomopolymers or copolymers and also mixtures and blends of suchplastics.

Suitable reinforcing materials are, for example, fibers and lay-ups,woven fabrics, mats, felts or nonwovens produced from fibers. Suitablefibers are, for example, natural fibers such as cellulose fibers, eg.cotton, sisal, jute, hemp, reed or flax fibers, synthetic fibers such aspolyester, polyurethane, polyamide, aramid or polyacrylonitrile fibers,metal fibers, preferably carbon fibers and in particular glass fibers,with the fibers being able to be provided with coupling agents and/orsizes. The type of reinforcing material depends on the purpose for whichthe moldings are to be used.

Suitable glass fibers, which can, as mentioned above, also be used inthe form of, for example, woven fabrics, mats, nonwovens and/orpreferably fiberglass rovings or chopped fiberglass made of low-alkali Eglasses and having a diameter of from 5 to 200 μm, preferably from 6 to15 μm, generally have a mean fiber length of from 0.05 to 1 mm,preferably from 0.1 to 0.5 mm, after incorporation into the PU moldingcompositions.

To produce moldings having, for example, a density of from 0.15 to 1.4g/cm³, it is particularly useful to employ combinations of a PU systemand glass mats, woven fabrics and/or lay-ups. For moldings having anoverall density of up to about 0.6 g/cm³ and a thickness up to about 5mm, suitable reinforcing materials are, for example, bulky, continuousglass mats, for example having glass weights per unit area of from 225to 650 g/m², which are very readily permeable on foaming the PU system,so that complete impregnation of the glass mats can be achieved. Themoldings produced by the process of the present invention can havereinforcing material contents, eg. glass contents, of up to 75% byweight, for example when woven glass fabrics or glass lay-ups are usedas additional or sole reinforcing material; on the other hand, if onlycontinuous glass mats are used, the glass content is lower because ofthe high volume of the mats and is up to about 45% by weight.

h) To produce the self-releasing, compact or cellular moldings whichcomprise polyisocyanate polyaddition products and may containreinforcing material, it can be advantageous for process orsystem-specific reasons to use additional auxiliaries. Examples of suchpossible auxiliaries are additional external and/or internal moldrelease agents, surface-active substances, foam stabilizers, cellregulators, lubricants, fillers, dyes, pigments, flame retardants,hydrolysis inhibitors, fungistatic and bacteriostatic substances ormixtures thereof and, particularly when producing moldings having acompacted surface zone and a cellular core using water as blowing agentin a closed mold with compaction, microporous activated carbon and/ormicroporous carbon molecular sieves as described in U.S. Pat. No.5,254,597, crystalline, microporous molecular sieves and/or crystallinesilicon oxide as described in U.S. Pat. No. 5,110,834, amorphousmicroporous silica gel as described in EP-A-0 513 573, condensates ofpolyhydroxyl compounds and ammonium carbonate and/or salts of amines andcarbon dioxide. Suitable additional mold release agents are, forexample, metal salts of stearic acid which can be prepared fromcommercially available stearic acid and can, without significantlyimpairing the release action, contain up to 10% by weight, preferably upto 5% by weight, of unsaturated or saturated carboxylic acids havingfrom 8 to 24 carbon atoms, eg. palmitic acid, oleic acid, ricinoleicacid etc.

Metals used for forming the metal salts of stearic acid are, forexample, alkali metals, preferably sodium and potassium, alkaline earthmetals, preferably magnesium and calcium, and in particular zinc. Metalsalts of stearic acid which are preferably used are zinc stearate,calcium stearate and sodium stearate or mixtures of at least twostearates. Particular preference is given to using a mixture of zinc,calcium and sodium stearates.

If the additional use of the metal salts of stearic acid as mold releaseagent proves to be advantageous, the metal stearates are advantageouslyused in an amount of up to 12% by weight, preferably from 0.1 to 8% byweight, based on the weight of the relatively high molecular weightcompounds containing at least two reactive hydrogen atoms (b).

Suitable surface-active substances are, for example, compounds whichserve to aid the homogenization of the starting materials and may alsobe suitable for regulating the cell structure. Examples which may bementioned are emulsifiers such as the sodium salts of castor oilsulfates or of fatty acids and also amine salts of fatty acids, eg.diethylamine oleate, diethanolamine stearate, diethanolaminericinoleate, salts of sulfonic acids, eg. alkali metal or ammonium saltsof dodecylbenzene- or dinaphthylmethane-disulfonic acid and ricinoleicacid; foam stabilizers such as siloxane-oxyalkylene copolymers and otherorganopolysiloxanes, ethoxylated alkylphenols, ethoxylated fattyalcohols, paraffin oils, castor oil or ricinoleic esters, turkey red oiland peanut oil and cell regulators such as paraffins, fatty alcohols anddimethylpolysiloxanes. Oligomeric polyacrylates having polyoxyalkyleneand fluoroalkane radicals as side groups are also suitable for improvingthe emulsifying action, the cell structure and/or stabilizing the foam.The surface-active substances are usually employed in amounts of from0.01 to 5 parts by weight, based on 10 parts by weight of the component(b). As lubricant, the addition of a ricinoleic polyester having amolecular weight of from 1500 to 3500, preferably from 2000 to 3000, hasbeen found to be particularly useful and this is advantageously used inan amount of from 0.5 to 10% by weight, preferably from 5 to 8% byweight, based on the weight of the component (b) or the components (b)and (c).

For the purposes of the present invention, fillers, in particularreinforcing fillers, are the customary organic and inorganic fillers andreinforcing materials known per se. Specific examples are: inorganicfillers such as glass spheres, siliceous minerals, for example sheetsilicates such as antigorite, serpentine, hornblends, amphiboles,chrysotile, talc, wollastonite, mica and synthetic silicates such asmagnesium aluminum silicate (Transpafill®); metal oxides such as kaolin,aluminum oxides, aluminum silicate, titanium oxides and iron oxides;metal salts such as chalk, barite; and inorganic pigments such ascadmium sulfide and zinc sulfide. Suitable organic fillers are, forexample: carbon black, melamine, rosin, cyclopentadienyl resins andgraft polymers. The fillers can be used either individually or inappropriate combinations among one another or with one another. It isalso possible to use fillers in combination with reinforcing materials.

The inorganic and/or organic fillers can be incorporated into thereaction mixture and, if they are used at all, are advantageously usedin an amount of from 0.5 to 50% by weight, preferably from 1 to 40% byweight, based on the weight of the components (a) to (c).

Suitable flame retardants are, for example, tricresyl phosphate,tris(2-chloroethyl) phosphate, tris(2-chloropropyl) phosphate,tris(1,3-dichloropropyl) phosphate, tris(2,3-dibromopropyl) phosphateand tetrakis(2-chloroethyl)ethylene diphosphate.

Apart from the abovementioned halogen-substituted phosphates, it is alsopossible to use inorganic flame retardants such as modified orunmodified red phosphorus, expanded graphite, hydrated aluminum oxide,antimony trioxide, arsenic oxide, ammonium polyphosphate and calciumsulfate or cyanuric acid derivatives such as melamine or mixtures of atleast two flame retardants such as expanded graphite and ammoniumpolyphosphate, ammonium polyphosphates and melamine and also, ifdesired, expanded graphite and/or starch for making the moldingsproduced according to the present invention flame resistant. In general,it has been found to be advantageous to use from 2 to 50 parts byweight, preferably from 5 to 25 parts by weight, of the flame retardantsor mixtures mentioned per 100 parts by weight of the components (a) to(c).

Further details regarding the abovementioned other customary auxiliariesand additives may be found in the specialist literature, for example themonograph by J. H. Saunders and K. C. Frisch, “High Polymers”, VolumeXVI, Polyurethanes, parts 1 and 2, Interscience Publishers 1962 and1964, or the Kunststoff-Handbuch, Polyurethane, Volume VII,Carl-Hanser-Verlag, Munich, Vienna, 1st and 2nd editions, 1966 and 1983.

To produce the compact or cellular moldings, the organic, modified orunmodified polyisocyanates (a), relatively high molecular weightcompounds containing at least two reactive hydrogen atoms (b) and, ifdesired, low molecular weight chain extenders and/or crosslinkers can bereacted in such amounts that the equivalence ratio of NCO groups of thepolyisocyanates (a) to the sum of the reactive hydrogen atoms of thecomponents (b) and, if used, (c) is 0.85-1.50:1, preferably 0.95-1.15:1and in particular 1.0-1.1:1.

To produce moldings comprising polyisocyanate polyaddition productscontaining isocyanurate groups, it is advantageous to use equivalenceratios of NCO groups of the polyisocyanates (a) to the sum of thereactive hydrogen atoms of the component (b) and, if used, (c) of1.6-30:1, preferably 1.6-15:1 and in particular 2.5-10:1.

The cellular or compact polyisocyanate polyaddition products of thepresent invention which may contain reinforcing material and preferablycontain bonded urethane or urethane and urea groups and possiblyisocyanurate groups or predominantly urea groups can be produced by theprepolymer process or preferably by the one-shot process using thelow-pressure technique or the high-pressure technique in open orpreferably closed, advantageously heatable molds, for example metalmolds made of, for example, aluminum, cast iron or steel or molds madeof fiber-reinforced polyester or epoxide molding compositions. Cellularand compact moldings comprising polyurethane or polyurethane-polyureaelastomers are produced, in particular, by means of the reactioninjection molding technique (RIM technique). These methods aredescribed, for example, by Piechota and Röhr in “Integralschaumstoff”,Carl-Hanser-Verlag, Munich, Vienna, 1975; D. J. Prepelka and J. L.Wharton in Journal of Cellular Plastics, March/April 1975, pages 87 to98, U. Knipp in Journal of Cellular Plastics, March/April 1973, pages 76to 84 and in the Kunststoff-Handbuch, Volume 7, Polyurethane, 2ndedition, 1983, Pages 333 ff.

It has been found to be particularly advantageous to employ thetwo-component method and to combine the formative components (b), (d)and, if desired, (c) and also (e) to (f) as the component (A) and to usethe organic polyisocyanates, modified polyisocyanates (a) or mixtures ofsaid polyisocyanates and, if desired, blowing agents as component (B).

The formative components can be mixed at from 15 to 80° C., preferablyfrom 20 to 55° C., and introduced into an open or closed mold which forproducing reinforced moldings can be lined beforehand with wovenfabrics, mats, felts, nonwovens and/or lay-ups as reinforcing material.To produce integral foams and cellular or compact elastomers, thereaction mixture can be introduced under superatmospheric pressure intothe closed mold.

Mixing can be carried out mechanically by means of a stirrer or stirringscrew or under high pressure in countercurrent injection processes. Themold temperature is advantageously from 20 to 120° C., preferably from30 to 80° C. and in particular from 45 to 60° C. If the moldings areproduced in a closed mold with compaction, eg. to form a compact surfacezone and a cellular core of the molding, it has been found to beadvantageous to employ degrees of compaction in the range from 1.2 to8.3, preferably from 1.6 to 6.0 and in particular from 2.0 to 4.0.

The cellular elastomers produced by the process of the present inventionhave densities of from about 0.76 to 1.1 g/cm³, preferably from 0.9 to1.0 g/cm³, with the density of products containing fillers and/or, inparticular, reinforced with glass mats being able to reach highervalues, eg. up to 1.4 g/cm³ and more. Moldings comprising such cellularelastomers are used, for example, in the automobile industry, forexample in automobile interiors as lining components, parcel shelves,trunk covers, dashboards and headrests, and as exterior components suchas rear spoilers, gutters and bumpers and also as rollers, slidingsunroofs and interior door linings for automobiles. Compact elastomershave densities of from about 1.0 to 1.1 g/cm³, with the productscontaining fillers and/or reinforcing material being able to havedensities up to 2.0 g/cm³ and more. Compact moldings of this type aresuitable, for example, in the automobile industry as buckets of seats,spare wheel recesses or engine splash guards.

The flexible, semirigid and rigid molding polyurethane foams produced bythe process of the present invention and also the correspondingpolyurethane integral foam moldings have a density of from 0.025 to 0.75g/cm³, with the densities of the molded PU foams being preferably from0.03 to 0.24 g/cm³ and in particular from 0.03 to 0.1 g/cm³ and thedensities of the PU integral foam moldings being preferably from 0.08 to0.75 g/cm³ and in particular from 0.24 to 0.6 g/cm³. The PU foammoldings and PU integral foam moldings can be used, for example, in thevehicle industry, eg. automobile, aircraft and shipbuilding industries,the furniture and sports article industries as, for example, paddingmaterials, eg. seats for automobiles, motorbikes or tractors, asheadrests, lining elements, housing components, consoles, cores andinternal protection for skis, roof frames and sunroofs in vehicles andwindow frames.

The invention is illustrated by the following examples.

EXAMPLE 1 Production of Cellular Polyurethane Molded Sheets Reinforcedwith Glass Mats

A Component

56.2 parts by weight of a polyoxypropylene polyol having a hydroxylnumber of 490 and prepared by propoxylation of an initiator mixture ofsucrose and glycerol in a weight ratio of 60:40,

4.5 parts by weight of glycerol,

7 parts by weight of a pentaerythritol-initiated polyoxyethylene polyolhaving a hydroxyl number of 630,

1.8 parts by weight of water,

0.9 part by weight of a stabilizer based on silicone (Stabilizer OS 340from Bayer AG, Germany),

1.0 part by weight of 1-methylimidazole,

0.8 part by weight of dimethyliminocyclohexane,

20.0 parts by weight of an monomeric alkyl epoxy stearate (Edenol

B35 from Henkel),

6.0 parts by weight of an internal mold release agent prepared byreacting one mol of polyisobutylenesuccinic anhydride having a meanmolecular weight M_(n) (number average) of the polyisobutylene radicalof 1000 and one mol of an ester of oleic acid/adipicacid/pentaerythritol having an OH number of 20 and an acid number of 23mg KOH/g. The reaction was carried out at 110° C. for 4 hours whileflushing with nitrogen. the solvent used was Edenol B33. After cooling,a low-viscosity liquid of the monoester in Edenol B35 (weight ratio 1:1)having an acid number of 13.7 mg KOH/g was obtained. The mold releaseagent displayed a pronounced ester band at 1737 cm⁻¹ in the IR spectrum,

1.8 parts by weight of black paste from ISL, Germany.

B Component

Mixture of diphenylmethane diisocyanates and polyphenyl-polymethylenepolyisocyanates having an NCO content of 31% by weight (raw MDI). Themixing ratio was 100:131.1.

When free-foamed at 25° C., the polyaddition mixture displayed thefollowing parameters

Cream time: 26 seconds

Rise time: 70 seconds

The free-foamed foam density was 79.5 g/l.

The molded sheets reinforced with glass mats were produced on ahigh-pressure metering unit model ®Puromat 30, fromElastogran-Maschinenbau, Straβlach bei M{umlaut over (u)}nchen, by theRIM technique in a metal mold heated to 56° C. and having the internaldimensions 4×60×300 mm, which was treated once at the beginning of theseries of experiments with the external mold release agent LS 1000 fromKl{umlaut over (u)}ber Chemie AG, Germany. Commercial glass mats havinga weight per unit area of from 450 to 600 g/m². were laid into the mold.

100 parts by weight of the A component and 130 parts by weight of the Bcomponent, each of which were at 25° C., were mixed by the RIM method inthe abovementioned high-pressure metering unit and injected into theclosed mold containing glass mats.

The pressure of the A component was 170 bar and that of the B componentwas 200 bar. The shot time was 2 seconds.

The molded sheet was removed from the mold after 120 seconds. It had adensity of 0.9 g/cm³ and when using a glass mat of 600 g/m² had a glasscontent of 20% by weight.

After 65 molded sheets had been able to be removed from the mold withoutproblems, the series of experiments was terminated.

The glass fiber-reinforced polyurethane sheets were subsequentlybackfoamed with a conventional semirigid foam in order to test adhesion.Even after 78 hours, the foam still adhered.

EXAMPLE 2 Production of Rigid Polyurethane Integral Foam Moldings

A Component

45.0 parts by weight of a trimethylolpropane-initiated polyoxypropylenepolyol having an OH number of 860,

10 parts by weight of a polyoxypropylene polyol having a hydroxyl numberof 400 and a functionality of 4.3 and prepared using an initiatormixture of sucrose, glycerol and water,

24 parts by weight of a 1,2-propanediol-initiated polyoxypropylenepolyol having a functionality of 2 and an OH number of 56,

1.1 parts by weight of additive SM from Bayer AG, Germany,

1.0 part by weight of silicone DG 193 from DOW Corning,

0.2 part by weight of phosphoric acid,

1.1 parts by weight of N,N-bis(dimethylaminopropyl)methylamine,

10.3 part by weight of 1-methylimidazole,

10.0 parts by weight of a glycerol-initiated polyoxypropylene polyolhaving a hydroxyl number of 400,

6.0 parts by weight of the mold release agent from Example 1.

B Component

Mixture of diphenylmethane diisocyanates and polyphenylpolymethylenepolyisocyanates having an NCO content of 31% by weight (raw MDI). Themixing ratio was 100:148.31.

When free-foamed at 200° C., the polyaddition mixture displayed thefollowing parameters:

Cream time: 42 seconds

Fiber time: 72 seconds

Rise time: 80 seconds

Foam density (free-foamed): 184 g/l

The machine times were

Cream time: 13 seconds

Fiber time: 35 seconds

Rise time: 42 seconds

Foam density (machine): 175 g/l

The rigid polyurethane integral foam materials were produced on ahigh-pressure metering unit model ®Puromat 30 fromElastogran-Maschinenbau, Straβlach bei M{umlaut over (u)}nchen, by theRIM technique in an aluminum mold for a spoiler which had been heated to50° C. The pressure of the A and B components was 150 bar. The airloading was 20%. The demolding time was 3 minutes. Before thecommencement of the experiment, the mold was treated with a customarywax-containing mold release agent Acmosil 35-3053 H from Acmos.Subsequently, 50 spoilers were produced without additional mold releaseagent.

EXAMPLE 3

A Component

36.2 parts by weight of a polyol which had been prepared as described inEP 0 554 590 by ring-opening of epoxidized soybean oil with glycol andhad an OH number of 253

28.8 parts by weight of castor oil having an OH number of 160,

26.8 parts by weight of a glycerol-initiated polyoxypropylene polyolhaving an OH number of 555 and prepared using boron trifluoride etherateas catalyst,

1.0 part by weight of water,

0.2 part by weight of Dabco 8154 from Air Products,

1.0 part by weight of an emulsifier as described in Example 12 of U.S.Pat. No. 5,106,875,

6 parts by weight of an internal mold release agent prepared byesterification of 1 mol of polyisobutylenesuccinic anhydride having amean molecular weight M_(n) of the polyisobutylene radical of 1000 with2 moles of a trimethylolpropane-initiated polyoxypropylene(86% byweight)-polyoxyethylene-(14% by weight) triol having a hydroxyl numberof 26, which had been mixed in a ratio of 1:1 with a polyoxypropylenepolyol which had been initiated using 1,2-propanediol and had an OHnumber of 105.

The moldings were produced on a high-pressure metering unit model®Puromat 30 by the RIM technique in an aluminum mold heated to 60° C.and having the internal dimensions 4×250×300 mm.

100 parts by weight of the A component and 140.6 parts by weight of theB component, which were each at 30° C., were mixed by the RIM techniquein the high-pressure metering unit described in Example 1 and injectedinto the closed mold.

The pressure of the A and B components was from 150 to 200 bar, at anair loading of the A component of 40% by volume. The shot time was 2seconds.

The molded sheet was removed from the mold after 90 seconds and had adensity of 1.15 g/cm³.

After production of 20 molded sheets which were able to be removed fromthe mold without problems, the series of experiments was terminated.

EXAMPLE 4

This example was carried out using a method similar to Example 3. Themold release agent used was 6 parts by weight of the copolymer describedin WO/07944, Example 1.1, page 9. After 50 removals, the series ofexperiments was terminated.

EXAMPLE 5

This example was carried out using a method similar to Example 1. Theinternal mold release agent was prepared by reacting one mole ofpolyisobutylenesuccinic anhydride (PIBSA) having a mean molecular weightM_(n) (number average) of the polyisobutylene radical of 1000 and 1 molof an ester of sorbitan monooleate. The two starting materials werestirred in a round-bottomed flask for 3 hours at an internal temperatureof 130-1400° C. under a nitrogen atmosphere. The final product had an OHnumber of 17 mg KOH/g and an acid number of 32 mg KOH/g. An amount of 5parts by weight, based on the polyol component, was used.

After producing 85 glass fiber-reinforced sheets having a length of 120cm, the series of experiments was terminated. After backfoaming of thesheets with a semirigid foam, the adhesion was still excellent after 120hours.

EXAMPLE 6

A Component:

58.6 parts by weight of a polyoxypropylene polyol having a hydroxylnumber of 490, and prepared by propoxylation of an initiator mixture ofsucrose and glycerol in a weight ratio of 60:40

20.0 parts by weight of a hydroxyl-containing alkylene oxide stearatefor improving the flow (®Edenor B33 from Henkel, Germany)

4.5 parts by weight of glycerol

3.8 parts by weight of black paste from ISL, Cologne

4.0 parts by weight of a pentaerythritol-initiated polyoxyethylenepolyol having a hydroxyl number of 630

0.8 part by weight of dimethylaminocyclohexane

1.4 parts by weight of water

0.9 part of a stabilizer based on silicone (stabilizer OS 340 from BAYERAG, Germany)

1.0 part by weight of 1-methylimidazole

5.0 parts by weight of an internal mold release agent prepared byesterifying 0.1 mol of polyisobutylenesuccinic anhydride having a meanmolecular weight M_(n) of the polyisobutylene radical of 1000 with 0.1mol of “Kraton Liquid® L-1203 Polymer” from Shell Chemicals having ahydroxyl number of 15 mg KOH/g. The reaction product had an acid numberof 10.0 mg of KOH/g. It was prepared in a three-neck flask at 145° C.,over a period of 4 hours.

The moldings were produced on a high-pressure metering unit model®Puromat 30 by the RIM technique in an aluminum mold heated to 60° C.and having the internal dimensions 4×250×300 mm.

100 parts by weight of the A component and 140.6 parts by weight of theB component, each of which were at 30° C., were mixed by the RIMtechnique in the high-pressure metering unit described in Example 1 andinjected into the closed mold.

The pressure of the A and B components was from 150 to 200 bar at an airloading of the A component of 40% by volume. The shot time was 2seconds.

The molded sheet was removed from the mold after 90 seconds. It had adensity of 1.15 g/cm³.

After producing 20 molded sheets which had been able to be removed fromthe mold without problems, the series of experiments was terminated.

B Component: As in Example 1

EXAMPLE 7

A Component:

58.6 parts by weight of a polyoxypropylene polyol having a hydroxylnumber of 490 and prepared by propoxylation of an initiator mixture ofsucrose and glycerol in a weight ratio of 60:40

20.0 parts by weight of a hydroxyl-containing alkylene oxide stearatefor improving the flow (®Edenor B33 from Henkel, Germany)

4.5 parts by weight of glycerol

3.8 parts by weight of black paste from ISL, Cologne

4.0 parts by weight of a pentaerythritol-initiated polyoxyethylenepolyol having a hydroxyl number of 630

0.8 part by weight of dimethylaminocyclohexane

1.4 parts by weight of water

0.9 part by weight of a stabilizer based on silicone (stabilizer OS 340from BAYER AG, Germany)

1.0 part by weight of 1-methylimidazole

5.0 parts by weight of an internal mold release agent prepared byesterification of 0.05 mol of MSA-polyisobutylene copolymer having amean molecular weight M_(n) of the polyisobutylene radical of 1000 with0.1 mol of “Kraton Liquid® L-1203 Polymer” from Shell Chemicals having ahydroxyl number of 15 mg KOH/g. The reaction product had an acid numberof 17.1 mg KOH/g. It was prepared in a three-neck flask at 145° C., overa period of 4 hours.

The moldings were produced on a high-pressure metering unit model®Puromat 30 by the RIM technique in an aluminum mold heated to 60° C.and having the internal dimensions 4×250×300 mm.

100 parts by weight of the A component and 140.6 parts by weight of theB component, each of which was at 30° C., were mixed by the RIMtechnique in the high-pressure metering unit described in Example 1 andinjected into the closed mold.

The pressure of the A and B components was from 150 to 200 bar, at anair loading of the A component of 40% by volume. The shot time was 2seconds.

The molded sheet was removed from the mold after 90 seconds. It had adensity of 1.15 g/cm³.

After producing 20 molded sheets which had been able to be removed fromthe mold without problems, the series of experiments was terminated.

B Component: As in Example 1

EXAMPLE 8

A Component:

58.6 parts by weight of a polyoxypropylene polyol having a hydroxylnumber of 490 and prepared by propoxylation of an initiator mixture ofsucrose and glycerol in a weight ratio of 60:40

20.0 parts by weight of a hydroxyl-containing alkylene oxide stearatefor improving the flow (®Edenor B33 from Henkel, Germany)

4.5 parts by weight of glycerol

3.8 parts by weight of black paste from ISL, Cologne

4.0 parts by weight of a pentaerythritol-initiated polyoxyethylenepolyol having a hydroxyl number of 630

0.8 part by weight of dimethylaminocyclohexane

1.4 parts by weight of water

0.9 part by weight of a stabilizer based on silicone (stabilizer OS 340from BAYER AG, Germany)

1.0 part by weight of 1-methylimidazole

5.0 parts by weight of an internal mold release agent prepared byesterification of 0.2 mol of polyisobutylenesuccinic anhydride with 0.1mol of “Kraton Liquid® L 2203 Polymer” from Shell Chemicals having ahydroxy equivalent weight of 1800. It was prepared in a three-neck flaskat 145° C., over a period of 4 hours.

The moldings were produced on a high-pressure metering unit model®Puromat 30 by the RIM technique in an aluminum mold heated to 60° C.and having the internal dimensions 4×250×300 mm.

100 parts by weight of A component and 140.6 parts by weight of the Bcomponent, each of which were at 30° C., were mixed by the RIM techniquein the high-pressure metering unit described in Example 1 and injectedinto the closed mold.

The pressure of the A and B components was from 150 to 200 bar, at anair loading of the A component of 40% by volume. The shot time was 2seconds.

The molded sheet was removed from the mold after 90 seconds. It had adensity of 1.15 g/cm³.

After producing 20 molded sheets which had been able to be removed fromthe mold without problems, the series of experiments was terminated.

B Component: as in Example 1

EXAMPLE 9

A Component:

58.6 parts by weight of a polyoxypropylene polyol having a hydroxylnumber of 490 and prepared by propoxylation of an initiator mixture ofsucrose and glycerol in a weight ratio of 60:40

20.0 parts by weight of a hydroxyl-containing alkylene oxide stearatefor improving the flow (®Edenor B33 from Henkel, Germany)

4.5 parts by weight of glycerol

3.8 parts by weight of black paste from ISL, Cologne

4.0 parts by weight of a pentaerythritol-initiated polyoxyethylenepolyol having a hydroxyl number of 630

0.8 part by weight of dimethylaminocyclohexane

1.4 parts by weight of water

0.9 part by weight of a stabilizer based on silicone (stabilizer OS 340from BAYER AG, Germany)

1.0 part by weight of 1-methylimidazole

5.0 parts by weight of an internal mold release agent prepared byesterification of 0.1 mol of polyisobutylenesuccinic succinic anhydridewith 0.1 mol of “Kraton Liquid® Polymer”EKP 207 from Shell Chemicalshaving a hydroxy equivalent weight of 6000. It was prepared in athree-neck flask at 145° C., over a period of 4 hours.

The moldings were produced on a high-pressure metering unit model®Puromat 30 by the RIM technique in an aluminum mold heated to 60° C.and having the internal dimensions 4×250×300 mm.

100 parts by weight of the A component and 140.6 parts by weight of theB component, each of which were at 30° C., were mixed by the RIMtechnique in the high-pressure metering unit described in Example 1 andinjected into the closed mold.

The pressure of the A and B components was from 150 to 200 bar, at anair loading of the A component of 40% by volume. The shot time was 2seconds.

The molded sheet was removed from the mold after 90 seconds. It had adensity of 1.15 g/cm³.

After producing 20 molded sheets which had been able to be removed fromthe mold without problems, the series of experiments was terminated.

B Component: As in Example 1

We claim:
 1. A process for producing self-releasing, compact or cellularmoldings comprising reacting a) organic and/or modified organicpolyisocyanates with b) at least one compound containing at least tworeactive hydrogen atoms and having a molecular weight of from 62 to10,000 and, optionally, c) chain extenders and/or crosslinkers in thepresence of d) internal mold release agents and in the presence orabsence of e) catalysts, f) blowing agents, g) reinforcing materials andh) auxiliaries in an open or closed mold, wherein the internal moldrelease agents (d) comprise diesters and/or monoesters of alkylsuccinicacids and/or diesters and/or monoesters of alkenylsuccinic acids.
 2. Aprocess as claimed in claim 1, wherein the alkyl or alkenyl groups ofthe alkylsuccinic or alkenylsuccinic diesters or monoesters have a meanmolecular weight (number average) M_(n) of from 250 to
 3000. 3. Aprocess as claimed in claim 2, wherein the alkyl groups of thealkylsuccinic or alkenylsuccinic acids or monesters/diesters are linearor branched and comprise polyisopropylene or polyisobutylene radicalsand the alkenyl groups comprise polyethenyl, polyisopropenyl orpolyisobutenyl radicals.
 4. A process as claimed in claim 3, wherein thealkyl groups comprise oligomers of propene and/or at least one branched1-olefin having from 4 to 10 carbon atoms and contain at least 3 olefinunits and have a mean molecular weight (M_(w)) of from 300 to 3000g/mol.
 5. A process as claimed in claim 1, wherein the alkylsuccinicand/or alkenylsuccinic acids is prepared by polymerization of a) from 20to 60 mol % of maleic acid or its anhydride, b) from 10 to 70 mol % ofat least one oligomer of propene or a branched 1-olefin having from 4 to10 carbon atoms, having a mean molecular weight M of from 300 to 5000,and c) from 1 to 50 mol % of at least one monoethylenically unsaturatedcompound which can be copolymerized with the monomers a) and b).
 6. Aprocess as claimed in claim 5, wherein the monomer c) is selected fromthe group consisting of monoethylenically unsaturatedC₃-C₁₀-monocarboxylic acids; linear 1-olefins having from 2 to 40 carbonatoms; and vinyl and alkyl allyl ethers having from 1 to 40 carbon atomsin the alkyl radical.
 7. A process as claimed in claim 1, wherein thealkylsuccinic or alkenylsuccinic diesters or monoesters are prepared byreacting alkylsuccinic acid or derivatives or alkenylsuccinic acid orderivatives with primary and/or secondary organic monoalcohols and/orpolyalcohols.
 8. A process as claimed in any of claim 1, wherein thealkylsuccinic or alkenylsuccinic diesters or monoesters are prepared byreacting alkylsuccinic or alkenylsuccinic anhydride with aliphaticmonools and/or polyols.
 9. A process as claimed in any of claim 1,wherein the alkylsuccinic or alkenylsuccinic diesters and/or monoestersare prepared by reacting alkylsuccinic and/or alkenylsuccinic acidand/or derivatives with monools or polyols selected from the group (A)consisting of a) alkanols having up to 40 carbon atoms; b) polyetherpolyols; c) polyester polyols; d) hydroxyl-containing natural materials;e) esters of at least trifunctional alcohols and fatty acids, in whichesters at least one hydroxyl group is free; and f) aminoalcohols and/orpolyols containing only tertiary amino groups.
 10. A process as claimedin any of claim 1, wherein the alkylsuccinic diesters or monoesters,alkenylsuccinic diesters or monoesters or mixtures of at least two ofthe diesters or monoesters or mixtures of diesters and monoesters areused in an amount of from 0.2 to 15 parts by weight per 100 parts byweight of the component (b).
 11. A process as claimed in any of claim 1,wherein the chain extenders or crosslinkers have a molecular weight ofless than
 500. 12. A process as claimed in claim 1, wherein the internalmold release agents comprise the reaction products ofpolyisobutylenesuccinic anhydride and/or polyisobutylenesuccinicanhydride and/or copolymers with an alcohol (A).
 13. A process asclaimed in claim 1, wherein the internal mold release agents comprisethe reaction products of polyisobutylenesuccinic anhydride and/orcopolymers with a combination of an alcohol (A) and an amine (B).
 14. Aprocess as claimed in claim 1, wherein the alkylsuccinic and/oralkenylsuccinic diesters and/or monoesters are treated with boron oxide,hydrated boron oxide, boric acid, boric esters, sulfur, phosphorusoxides, epoxides, episulfides, amines and/or alkaline earth metal salts.15. A process as claimed in claim 1, wherein the reinforcing materialsg) comprise fibers or lay-ups, woven fabrics, mats, felts or nonwovensbased on glass, carbon, metal, polymer and/or natural fibers.